EP2014755B1 - Method of cleaning dishware - Google Patents
Method of cleaning dishware Download PDFInfo
- Publication number
- EP2014755B1 EP2014755B1 EP08156229A EP08156229A EP2014755B1 EP 2014755 B1 EP2014755 B1 EP 2014755B1 EP 08156229 A EP08156229 A EP 08156229A EP 08156229 A EP08156229 A EP 08156229A EP 2014755 B1 EP2014755 B1 EP 2014755B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- alkyl
- cleaning
- dishware
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Revoked
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004140 cleaning Methods 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 169
- 239000007788 liquid Substances 0.000 claims abstract description 90
- 239000003599 detergent Substances 0.000 claims abstract description 65
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 60
- -1 polypropylene Polymers 0.000 claims description 68
- 239000004094 surface-active agent Substances 0.000 claims description 65
- 229920002873 Polyethylenimine Polymers 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000006116 polymerization reaction Methods 0.000 claims description 39
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 37
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 230000002209 hydrophobic effect Effects 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 23
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 229920001567 vinyl ester resin Polymers 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 229920001290 polyvinyl ester Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- 230000007812 deficiency Effects 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 2
- 229940079593 drug Drugs 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 238000002483 medication Methods 0.000 claims 1
- 239000004519 grease Substances 0.000 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000002904 solvent Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 24
- 238000004851 dishwashing Methods 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 15
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 6
- 239000003752 hydrotrope Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- RQHGZNBWBKINOY-PLNGDYQASA-N (z)-4-tert-butylperoxy-4-oxobut-2-enoic acid Chemical compound CC(C)(C)OOC(=O)\C=C/C(O)=O RQHGZNBWBKINOY-PLNGDYQASA-N 0.000 description 4
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 4
- VNJISVYSDHJQFR-UHFFFAOYSA-N tert-butyl 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOC(C)(C)C VNJISVYSDHJQFR-UHFFFAOYSA-N 0.000 description 4
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 3
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 235000019589 hardness Nutrition 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 3
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 2
- RAWISQFSQWIXCW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)CC RAWISQFSQWIXCW-UHFFFAOYSA-N 0.000 description 2
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 2
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 description 2
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 description 2
- 0 CC(CC(*)N)C(*)(C(C)C(C)C(C=C(C)[C@](COC(C)(C)*)C(C)(C)C(C)(C)OCCC(C)(C)O)O)N Chemical compound CC(CC(*)N)C(*)(C(C)C(C)C(C=C(C)[C@](COC(C)(C)*)C(C)(C)C(C)(C)OCCC(C)(C)O)O)N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical group CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- UYDGECQHZQNTQS-UHFFFAOYSA-N 2-amino-4,6-dimethylpyridine-3-carboxamide Chemical compound CC1=CC(C)=C(C(N)=O)C(N)=N1 UYDGECQHZQNTQS-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-FOQJRBATSA-N 59096-14-9 Chemical compound CC(=O)OC1=CC=CC=C1[14C](O)=O BSYNRYMUTXBXSQ-FOQJRBATSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CZNJCCVKDVCRKF-UHFFFAOYSA-N Benzyl sulfate Chemical class OS(=O)(=O)OCC1=CC=CC=C1 CZNJCCVKDVCRKF-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FVFCLQXLNHZGJI-UHFFFAOYSA-N CN(C)CCOC(C(CI)I)=O Chemical compound CN(C)CCOC(C(CI)I)=O FVFCLQXLNHZGJI-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 101000605014 Homo sapiens Putative L-type amino acid transporter 1-like protein MLAS Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 102100038206 Putative L-type amino acid transporter 1-like protein MLAS Human genes 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- IHRIVUSMZMVANI-UHFFFAOYSA-N azane;2-methylbenzenesulfonic acid Chemical compound [NH4+].CC1=CC=CC=C1S([O-])(=O)=O IHRIVUSMZMVANI-UHFFFAOYSA-N 0.000 description 1
- LUAVFCBYZUMYCE-UHFFFAOYSA-N azanium;2-propan-2-ylbenzenesulfonate Chemical compound [NH4+].CC(C)C1=CC=CC=C1S([O-])(=O)=O LUAVFCBYZUMYCE-UHFFFAOYSA-N 0.000 description 1
- HDMGIDHAXIXUIQ-UHFFFAOYSA-N azanium;3,4-dimethylbenzenesulfonate Chemical compound [NH4+].CC1=CC=C(S([O-])(=O)=O)C=C1C HDMGIDHAXIXUIQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001804 chlorine Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- WRZCPVUJXKDEFF-UHFFFAOYSA-N cyclohexane;methanamine Chemical compound NC.NC.C1CCCCC1 WRZCPVUJXKDEFF-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- BZCOSCNPHJNQBP-OWOJBTEDSA-N dihydroxyfumaric acid Chemical compound OC(=O)C(\O)=C(/O)C(O)=O BZCOSCNPHJNQBP-OWOJBTEDSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940098895 maleic acid Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- WHSXTWFYRGOBGO-UHFFFAOYSA-N o-cresotic acid Natural products CC1=CC=CC(C(O)=O)=C1O WHSXTWFYRGOBGO-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
-
- C11D2111/14—
Definitions
- the present invention relates to a method of cleaning dishware with a liquid detergent composition comprising an amphiphilic graft polymer to provide improved baked-on grease cleaning from dish surfaces and improved suds profile.
- Grease cleaning with liquid detergents poses an ongoing problem for consumers. Consumers utilizing liquid detergent as a light-duty liquid dishwashing detergent composition tend to wash greasy, difficult to clean items at the end of their washing experience, after easier to clean items such as glasses and flatware are cleaned. Light-duty liquid dishwashing detergent compositions require a high suds profile while providing grease cleaning.
- the method of the present invention is highly efficient in removing grease and in particular the more difficult baked-on grease layer.
- this baked-on grease is characterized by a higher hydrophobicity.
- the removal of such baked-on grease therefore requires surfactants with strong hydrophobic properties in order to penetrate and fluidify efficiently the grease layer and/or requires very high level of total surfactants.
- amphiphilic graft polymer of the present invention improves the suds profile of the light-duty liquid dishwashing detergent composition to be used in the method of the present invention. It increases suds mileage, especially in soft water.
- the present invention teaches a method of washing dishes with a liquid detergent composition comprising a specific amphiphilic graft polymer.
- the present application relates to a method of cleaning dishware with a liquid detergent composition comprising an amphiphilic grafted polymer and an alkoxylated polyethyleneimine polymer according to claim 1.
- the method of cleaning dishware of the present invention surprisingly provides improved grease cleaning, especially on baked-on grease while maintaining acceptable levels of total amount of such cleaning and improved suds profile in a liquid dishwashing detergent composition.
- greye means materials comprising at least in part (i.e., at least 0.5 wt% by weight of the grease) saturated and unsaturated fats and oils, preferably oils and fats derived from animal sources such as beef and/or chicken.
- aked-on grease means materials comprising grease exposed to increased temperatures in a standard oven, convection oven, toaster oven, microwave oven, stove top heating using a frying pan, wok, hot plate, electric griddle, or other known cooking appliances used to heat food during cooking.
- Suds profile means amount of sudsing (high or low) and the persistence of sudsing (sustained or prevention) throughout the washing process resulting from the use of the liquid detergent composition of the present composition.
- Liquid dishwashing detergent compositions require high sudsing and sustained suds. This is particularly important with respect to liquid dishwashing detergent compositions as the consumer uses high sudsing as an indicator of the performance of the detergent composition.
- the consumer in a liquid dishwashing detergent composition also uses the sudsing profile as an indicator that the wash solution still contains active detergent ingredients. The consumer usually renews the wash solution when the sudsing subsides.
- a low sudsing liquid dishwashing detergent composition formulation will tend to be replaced by the consumer more frequently than is necessary because of the low sudsing level.
- dishware means a surface such as dishes, glasses, pots, pans, baking dishes and flatware made from ceramic, china, metal, glass, plastic (polyethylene, polypropylene, polystyrene, etc.) and wood.
- light-duty liquid dishwashing detergent composition refers to those compositions that are employed in manual (i.e. hand) dishwashing. Such compositions are generally high sudsing or foaming in nature.
- cleaning means applying to a surface for the purpose of cleaning, and/or disinfecting.
- the present invention is directed to a process of cleaning a dishware with a light duty liquid composition comprising the amphiphilic graft polymer and alkoxylated polyethyleneimine according to claim 1.
- Said process comprises the steps of applying said composition onto said dishware, typically in diluted or neat form and rinsing or leaving said composition to dry on said surface without rinsing said surface.
- liquid composition in its neat form, it is meant herein that said liquid composition is applied directly onto the surface to be treated without undergoing any dilution by the user (immediately) prior to the application.
- diluted form it is meant herein that said liquid composition is diluted by the user with an appropriate solvent, typically with water.
- solvent typically with water.
- substantially quantities it is meant usually 5 to 20 liters.
- the composition herein can be applied in its diluted form.
- Soiled dishes are contacted with an effective amount, typically from 0.5 ml to 20 ml (per 25 dishes being treated), preferably from 3ml to 10 ml, of the liquid detergent composition of the present invention diluted in water.
- the actual amount of liquid detergent composition used will be based on the judgment of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredients in the composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
- the particular product formulation in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product. Suitable examples may be seen below in Table A.
- a liquid detergent composition of the invention is combined with from 2000 ml to 20000 ml, more typically from 5000 ml to 15000 ml of water in a sink having a volumetric capacity in the range of from 1000 ml to 20000 ml, more typically from 5000 ml to 15000 ml.
- the soiled dishes are immersed in the sink containing the diluted compositions then obtained, where contacting the soiled surface of the dish with a cloth, sponge, or similar article cleans them.
- the cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranged from 1 to 10 seconds, although the actual time will vary with each application and user.
- the contacting of cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
- Another method of the present invention will comprise immersing the soiled dishes into a water bath or held under running water without any liquid dishwashing detergent.
- a device for absorbing liquid dishwashing detergent such as a sponge, is placed directly into a separate quantity of undiluted liquid dishwashing composition for a period of time typically ranging from 1 to 5 seconds.
- the absorbing device, and consequently the undiluted liquid dishwashing composition is then contacted individually to the surface of each of the soiled dishes to remove said soiling.
- the absorbing device is typically contacted with each dish surface for a period of time range from 1 to 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
- the contacting of the absorbing device to the dish surface is preferably accompanied by concurrent scrubbing.
- composition used in the method according to the present invention is formulated as a liquid light-duty liquid dishwashing detergent composition comprising an amphiphilic graft polymer and alkoxylated polyethyleneimine polymer.
- amphiphilic graft polymer of the present invention is amphiphilic graft polymer of the present invention.
- amphiphilic graft polymer will typically be present in the composition of the present invention at a level of from 0.01 wt% to 5.0 wt%, preferably from 0.1 wt% to 2.0 wt%, more preferably from 0.2% to 1.5% by weight of the composition.
- the mean molecular weight Mw of the graft polymers is from 3000 to 100 000, preferably from 6000 to 45 000 and more preferably from 8000 to 30 000.
- the amphiphilic character and the block polymer structure of the graft polymers is particularly marked.
- the graft polymers also have only a low content of ungrafted polyvinyl ester (B). In general, they comprise 10% by weight, preferably 7.5% by weight and more preferably 5% by weight of ungrafted polyvinyl ester (B).
- the graft polymers are soluble in water or in water/alcohol mixtures (for example a 25% by weight solution of diethylene glycol monobutyl ether in water). They have pronounced, low cloud points which, for the graft polymers soluble in water at up to 50°C, are generally 95°C, preferably 85°C and more preferably 75°C, and, for the other graft polymers in 25% by weight diethylene glycol monobutyl ether, generally 90°C, preferably from 45 to 85°C.
- amphiphilic graft polymers have preferably (A) from 20% to 70% by weight of a water-soluble polyalkylene oxide as a graft base and (B) side chains formed by free-radical polymerization of from 30% to 80% by weight of a vinyl ester component composed of
- they comprise from 25% to 60% by weight of the graft base (A) and from 40% to 75% by weight of the polyvinyl ester component (B).
- Water-soluble polyalkylene oxides suitable for forming the graft base (A) are in principle all polymers based on C2-C4-alkylene oxides which comprise at least 50% by weight, preferably at least 60% by weight, more preferably at least 75% by weight of ethylene oxide in copolymerized form.
- the polyalkylene oxides (A) preferably have a low polydispersity Mw/Mn. Their polydispersity is preferably 1.5.
- the polyalkylene oxides (A) may be the corresponding polyalkylene glycols in free form, i.e. with OH end groups, but they may also be capped at one or both end groups. Suitable end groups are, for example, C1-C25-alkyl, phenyl and C1-C14-alkylphenyl groups.
- polyalkylene oxides (A) include:
- Preferred graft bases (A) are the polyethylene glycols (A1).
- the side chains of the graft polymers are formed by polymerization of a vinyl ester component (B) in the presence of the graft base (A).
- the vinyl ester component (B) may consist advantageously of (B1) vinyl acetate or vinyl propionate or of mixtures of vinyl acetate and vinyl propionate, particular preference being given to vinyl acetate as the vinyl ester component (B).
- the side chains of the graft polymer can also be formed by copolymerizing vinyl acetate and/or vinyl propionate (B1) and a further ethylenically unsaturated monomer (B2).
- the fraction of monomer (B2) in the vinyl ester component (B) may be up to 30% by weight, which corresponds to a content in the graft polymer of (B2) of 24% by weight.
- Suitable comonomers (B2) are, for example, monoethylenically unsaturated carboxylic acids and dicarboxylic acids and their derivatives, such as esters, amides and anhydrides, and styrene. It is of course also possible to use mixtures of different comonomers.
- (meth)acrylic acid C 1 -C 12 -alkyl and hydroxy-C 2 -C 12 -alkyl esters of (meth)acrylic acid, (meth)acrylamide, N-C 1 -C 12 -alkyl(meth)acrylamide, N,N-di(C 1 -C 6 -alkyl)(meth)acrylamide, maleic acid, maleic anhydride and mono(C 1 -C 12 -alkyl)esters of maleic acid.
- Preferred monomers (B2) are the C 1 -C 8 -alkyl esters of (meth)acrylic acid and hydroxyethyl acrylate, particular preference being given to the C 1 -C 4 -alkyl esters of (meth)acrylic acid.
- Very particularly preferred monomers (B2) are methyl acrylate, ethyl acrylate and in particular n-butyl acrylate.
- the content of graft polymers in (B2) is preferably from 0.5% to 20% by weight, more preferably from 1% to 15% by weight and most preferably from 2% to 10% by weight.
- the graft polymers are advantageously obtainable by polymerizing a vinyl ester component (B) composed of vinyl acetate and/or vinyl propionate (B1) and, if desired, a further ethylenically unsaturated monomer (B2), in the presence of a water-soluble polyalkylene oxide (A), a free radical-forming initiator (C) and, if desired, up to 40% by weight, based on the sum of components (A), (B) and (C), of an organic solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomer (B) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polyalkylene oxide (A).
- a vinyl ester component (B) composed of vinyl acetate and/or vinyl propionate (B1) and, if desired, a further ethyl
- a vinyl ester component (B) composed of (B1) from 70% to 100% by weight of vinyl acetate and/or vinyl propionate and (B2) from 0 to 30% by weight of a further ethylenically unsaturated monomer and from 20% to 70% by weight of a water-soluble polyalkylene oxide (A) of mean molar mass M n of from 1500 to 20 000.
- the amount of initiator (C) is preferably from 0.2% to 5% by weight, in particular from 0.5% to 3.5% by weight, based in each case on component (B).
- the steady-state concentration of radicals present at the mean polymerization temperature is substantially constant and the graft monomer (B) is present in the reaction mixture constantly only in low concentration (for example of not more than 5% by weight). This allows the reaction to be controlled, and graft polymers can be prepared in a controlled manner with the desired low degree of branching and the desired low polydispersity.
- mean polymerization temperature is intended to mean here that, although the process is substantially isothermal, there may, owing to the exothermicity of the reaction, be temperature variations which are preferably kept within the range of+/- 10°C, more preferably in the range of +/- 5°C.
- the free radical-forming initiator (C) at the mean polymerization temperature should have a decomposition half-life of from 40 to 500 min, preferably from 50 to 400 min and more preferably from 60 to 300 min.
- the initiator (C) and the graft monomer (B) are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and graft monomer (B) is present in the reaction mixture.
- the proportion of undecomposed initiator in the overall reaction mixture is preferably ⁇ 15% by weight, in particular ⁇ 10% by weight, based on the total amount of initiator metered in during the monomer addition.
- the mean polymerization temperature is appropriately in the range from 50°C to 140°C, preferably from 60°C to 120°C and more preferably from 65°C to 110°C.
- Suitable initiators (C) whose decomposition half-life in the temperature range from 50°C to 140°C is from 20 to 500 min are:
- examples of particularly suitable initiators (C) are:
- Preferred initiators (C) are O-C 4 -C 12 -acylated derivatives of tert-C 4 -C 5 -alkyl hydroperoxides, particular preference being given to tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.
- Particularly advantageous polymerization conditions can be established effortlessly by precise adjustment of initiator (C) and polymerization temperature.
- the preferred mean polymerization temperature in the case of use of tert-butyl peroxypivalate is from 60°C to 80°C, and, in the case oftert-butyl peroxy-2-ethylhexanoate, from 80°C to 100°C.
- the inventive polymerization reaction can be carried out in the presence of small amounts of an organic solvent (D). It is of course also possible to use mixtures of different solvents (D). Preference is given to using water-soluble or water-miscible solvents.
- a solvent (D) used as a diluent, generally from 1% to 40% by weight, preferably from 1% to 35% by weight, more preferably from 1.5% to 30% by weight, most preferably from 2% to 25% by weight, based in each case on the sum of the components (A), (B) and (C), are used.
- Suitable solvents (D) include:
- the solvents (D) are advantageously those solvents which are also used to formulate the inventive graft polymers for use (for example in washing and cleaning compositions) and can therefore remain in the polymerization product.
- these solvents are polyethylene glycols having 2-15 ethylene glycol units, polypropylene glycols having 2-6 propylene glycol units and in particular alkoxylation products of C 6 -C 8 -alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).
- alkoxylation products of C 8 -C 16 -alcohols with a high degree of branching which allow the formulation of polymer mixtures which are free-flowing at 40-70°C and have a very low polymer content at comparatively low viscosity.
- the branching may be present in the alkyl chain of the alcohol and/or in the polyalkoxylate moiety (copolymerization of at least one propylene oxide, butylene oxide or isobutylene oxide unit).
- alkoxylation products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide, C 13 /C 15 oxo alcohol or C12/C 14 or C 16 /C 18 fatty alcohol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide, preference being given to 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide.
- polyalkylene oxide (A), graft monomer (B1) and, if appropriate, (B2), initiator (C) and, if appropriate, solvent (D) are heated to the selected mean polymerization temperature in a reactor.
- the polymerization is carried out in such a way that an excess of polymer (polyalkylene oxide (A) and formed graft polymer) is constantly present in the reactor.
- the quantitative ratio of polymer to ungrafted monomer and initiator is generally ⁇ 10:1, preferably ⁇ 15:1 and more preferably ⁇ 20:1.
- the polymerization process according to the invention can in principle be carried out in various reactor types.
- the reactor used is preferably a stirred tank in which the polyalkylene oxide (A), if appropriate together with portions, of generally up to 15% by weight of the particular total amount, of graft monomers (B), initiator (C) and solvent (D), are initially charged fully or partly and heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are metered in, preferably separately.
- the remaining amounts of (B), (C) and, if appropriate, (D) are metered in preferably over a period of ⁇ 2 h, more preferably of ⁇ 4 h and most preferably of ⁇ 5 h.
- the entire amount of polyalkylene oxide (A) is initially charged as a melt and the graft monomers (B1) and, if appropriate, (B2), and also the initiator (C) present preferably in the form of a from 10 to 50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled such that the selected polymerization temperature, on average during the polymerization, is maintained with a range of especially +/- 10°C, in particular +/- 5°C.
- the procedure is as described above, except that solvent (D) is metered in during the polymerization in order to limit the viscosity of the reaction mixture. It is also possible to commence with the metered addition of the solvent only at a later time with advanced polymerization, or to add it in portions.
- the polymerization can be effected under standard pressure or at reduced or elevated pressure.
- the boiling point of the monomers (B) or of any diluent (D) used is exceeded at the selected pressure, the polymerization is carried out with reflux cooling.
- Aqueous Liquid Carrier Aqueous Liquid Carrier
- the liquid detergent compositions herein further contain from 30% to 80% of an aqueous liquid carrier in which the other essential and optional compositions components are dissolved, dispersed or suspended. More preferably the aqueous liquid carrier will comprise from 45% to 70%, more preferable from 45% to 65% of the compositions herein.
- the aqueous liquid carrier may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (20°C - 25°C) and which may also serve some other function besides that of an inert filler. Such materials can include, for example, hydrotropes and solvents, discussed in more detail below.
- the water in the aqueous liquid carrier can have a hardness level of about 2-30 gpg ("gpg" is a measure of water hardness that is well known to those skilled in the art, and it stands for "grains per gallon").
- the liquid detergent composition may have any suitable pH.
- the pH of the composition is adjusted to between 4 and 14. More preferably the composition has pH of between 6 and 13, most preferably between 6 and 10.
- the pH of the composition can be adjusted using pH modifying ingredients known in the art.
- liquid detergent compositions of the present invention are preferably thickened and have viscosity of greater than 500 cps, when measured at 20°C. More preferably the viscosity of the composition is between 500 and 1100 cps.
- a preferred further ingredient of the hand dishwashing composition of the present invention is a surfactant selected from nonionic, anionic, cationic surfactants, ampholytic, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof.
- Surfactants can be comprised at a level of from 1.0% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 25% to 40% by weight preferably from 30% to 38% by weight of the liquid detergent composition.
- Non-limiting examples of optional surfactants are discussed below.
- High levels of surfactants in particular high levels of anionic surfactants and/or hydrophobic surfactants, which may be desired for high grease cleaning performance, especially on more hydrophobic greases, cause instability of the dishwashing compositions.
- High levels of hydrophobic surfactants furthermore cause also suds suppression.
- amphiphilic graft polymer of the present invention is highly effective in producing highly effective grease cleaning, especially on more hydrophobic greases, without having to resort to extreme levels (eg above 35-40%) of total surfactant, and/or extreme levels of hydrophilic (C12-C14 chain) anionic surfactant (eg above 25-30%) and/or high levels (eg above 5%) of hydrophobic surfactants (NI surfactants and/or >14C chain anionic surfactants).
- NI surfactants and/or >14C chain anionic surfactants hydrophobic surfactants
- the addition of the amphiphilic graft polymer of the present invention allows to obtain the same or even better grease cleaning and sudsing performances without the addition of high levels of these surfactants.
- the composition to be used in the method of the present invention will comprise an anionic surfactant.
- anionic surfactants are the sulphate and surlfonate surfactants, more preferred are the alkyl sulphonates and paraffin sulphonates, even more preferred is linear alkyl sulphonate.
- the sulphate or sulphonate surfactant is typically present at a level of at least 5%, preferably from 5% to 40% and more preferably from 15% to 30% and even more preferably at 15% to 25% by weight of the liquid detergent composition.
- Suitable sulphate or sulphonate surfactants for use in the compositions herein include water-soluble salts or acids of C 10 -C 14 alkyl or hydroxyalkyl, sulphate or sulphonates.
- Suitable counterions include hydrogen, alkali metal cation or ammonium or substituted ammonium, but preferably sodium.
- hydrocarbyl chain is branched, it preferably comprises C 1-4 alkyl branching units.
- the average percentage branching of the sulphate or sulphonate surfactant is preferably greater than 30%, more preferably from 35% to 80% and most preferably from 40% to 60% of the total hydrocarbyl chains.
- the sulphate or sulphonate surfactants may be selected from C 11 -C 18 alkyl benzene sulphonates (LAS), C 8 -C 20 primary, branched-chain and random alkyl sulphates (AS); C 10 -C 18 secondary (2,3) alkyl sulphates; C 10 -C 18 alkyl alkoxy sulphates (AE x S) wherein preferably x is from 1-30; C 10 -C 18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; mid-chain branched alkyl sulphates as discussed in US 6,020,303 and US 6,060,443 ; mid-chain branched alkyl alkoxy sulphates as discussed in US 6,008,181 and US 6,020,303 ; modified alkylbenzene sulphonate (MLAS) as discussed in WO 99/05243 , WO 99/05242 , WO 99/05244 ,
- the paraffin sulphonates may be monosulphonates or disulphonates and usually are mixtures thereof, obtained by sulphonating paraffins of 10 to 20 carbon atoms.
- Preferred sulphonates are those of C12-18 carbon atoms chains and more preferably they are C14-17 chains.
- Paraffin sulphonates that have the sulphonate group(s) distributed along the paraffin chain are described in US2,503,280 ; US2,507,088 ; US3, 260,744 ; US 3,372 188 and in DE 735 096 .
- Alkyl glyceryl sulphonate surfactants and/or alkyl glyceryl sulphate surfactants generally used have high monomer content (greater than 60 wt% by weight of the alkyl glycerol sulphonate surfactant).
- oligomer includes dimer, trimer, quadrimer, and oligomers up to heptamers of alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant.
- Minimization of the monomer content may be from 0 wt% to about 60 wt%, from 0 wt% to about 55 wt%, from 0 wt% to about 50 wt%, from 0 wt% to about 30 wt%, by weight of the alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant present.
- alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant for use herein include such surfactants having an alkyl chain length from C 10-40 , C 10-22 , C 12-18 , and C 16-18 .
- the alkyl chain may be branched or linear, wherein when present, the branches comprise a C 1-4 alkyl moiety, such as methyl (C 1 ) or ethyl (C 2 ).
- the structures of suitable alkyl glyceryl sulphonate surfactant oligomers that may be used herein include (A) dimers; (B) trimers, and (C) tetramers:
- R in the above structures (A)-(C) is from C 10-40 , C 10-22 , C 12-18 , and C 16-18 .
- the alkyl chain may be branched or linear, wherein when present, the branches comprise a C 1-4 alkyl moiety, such as methyl (C 1 ) or ethyl (C 2 ).
- the corresponding alkyl glyceryl sulphate surfactant oligomers may also have similar structures with the SO 3 - moiety being an OSO 3 - moiety.
- the alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant oligomer content may be between 40wt% and 100 wt%, 45 wt% and 100 wt%, 50 wt% and 100wt%, 70wt% and 100wt% by weight of the alkyl glycerol sulphonate surfactant and/or alkyl glyceryl sulphate surfactant.
- the "oligomer content” means the sum of the alkyl glyceryl sulphonate surfactant oligomers and/or alkyl glyceryl sulphate surfactant oligomers, such as dimers, trimers, quadrimers, and above (heptamers) present in the alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant. More specifically, as shown below in Table I, nonlimiting examples of alkyl glyceryl sulphonate surfactant oligomer content demonstrates the weight percent of oligomers present and the minimization of the monomer content of the alkyl glyceryl sulphonate surfactant.
- the alkyl glyceryl sulphonate surfactant is optionally present at a level of at least 10%, more preferably from 10% to 40% and most preferably from 10% to 30% by weight of the composition.
- An optional component used in the liquid detergent composition of the present invention is dialkyl sulfosuccinates.
- the dialkyl sulfosuccinates may be a C 6-15 linear or branched dialkyl sulfosuccinate.
- the alkyl moieties may be symmetrical (i.e., the same alkyl moieties) or asymmetrical (i.e., different alkyl moieties).
- the alkyl moiety is symmetrical.
- the dialkyl sulfosuccinates may be present in the liquid detergent composition from 0.5% to 10% by weight of the composition.
- Nonionic surfactants are generally considered as hydrophobic surfactants.
- Nonionic surfactant when present, is comprised in a typical amount of from 0.1% to 20%, preferably 0.5% to 10% by weight of the liquid detergent composition.
- Suitable nonionic surfactants include the condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide.
- the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from 2 to 18 moles of ethylene oxide per mole of alcohol.
- the number of mole of ethylene oxide per mole of alcohol is usually between 2 and 6 for more hydrophobic nonionic surfactants.
- Most suitable hydrophobic surfactants for grease cleaning are the solubilising nonionic surfactants described in US 2005/0107275 published on May 19, 2005 by the Procter & Gamble Company, pages 2-3, paragraphs [0018] to [0031].
- alkylpolyglycosides having the formula R 2 O(C n H 2n O) t (glycosyl) x (formula (III)), wherein R 2 of formula (III) is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n of formula (III) is 2 or 3, preferably 2; t of formula (III) is from 0 to 10, preferably 0; and x of formula (III) is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
- the glycosyl is preferably derived from glucose.
- fatty acid amide surfactants having the formula (IV): wherein R 6 of formula (IV) is an alkyl group containing from 7 to 21, preferably from 9 to 17, carbon atoms and each R 7 of formula (IV) is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and -(C 2 H 4 O) x H where x of formula (IV) varies from 1 to 3.
- Preferred amides are C 8 -C 20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
- Cationic surfactants when present in the composition, are present in an effective amount, more preferably from 0.1 % to 20%, by weight of the liquid detergent composition.
- Suitable cationic surfactants are quaternary ammonium surfactants. Suitable quaternary ammonium surfactants are selected from the group consisting of mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyehthyl or hydroxypropyl groups.
- Another preferred cationic surfactant is an C 6 -C 18 alkyl or alkenyl ester of a quaternary ammonium alcohol, such as quaternary chlorine esters.
- the cationic surfactants have the formula (V): wherein R1 of formula (V) is C 8 -C 18 hydrocarbyl and mixtures thereof, preferably, C 8-14 alkyl, more preferably, C 8 , C 10 or C 12 alkyl, and X of formula (V) is an anion, preferably, chloride or bromide.
- Preferred ingredients for the liquid detergent compositions are amine oxides surfactants which typically herein may be comprised at a level of from 0.1% to 15% by weight, preferably from 3.0% to 10% by weight of the liquid detergent composition.
- the amine oxide may have a linear or mid-branched alkyl moiety.
- Linear amine oxides include water-soluble amine oxides containing one C 8-18 alkyl moiety and 2 moieties selected from the group consisting of C 1-3 alkyl groups and C 1-3 hydroxyalkyl groups; water-soluble phosphine oxides containing one C 10-18 alkyl moiety and 2 moieties selected from the group consisting of C 1-3 alkyl groups and C 1-3 hydroxyalkyl groups; and water-soluble sulfoxides containing one C 10-18 alkyl moiety and a moiety selected from the group consisting of C 1-3 alkyl and C 1-3 hydroxyalkyl moieties.
- Preferred amine oxide surfactants have formula (VI): wherein R 3 of formula (VI) is an linear C 8-22 alkyl, linear C 8-22 hydroxyalkyl, C 8-22 alkyl phenyl group, and mixtures thereof; R 4 of formula (VI) is an C 2-3 alkylene or C 2-3 hydroxyalkylene group or mixtures thereof; x is from 0 to about 3; and each R 5 of formula (VI) is an C 1-3 alkyl or C 1-3 hydroxyalkyl group or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups.
- the R 5 groups of formula (VI) may be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
- the linear amine oxide surfactants in particular may include linear C 10 -C 18 alkyl dimethyl amine oxides and linear C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
- Preferred amine oxides include linear C 10 , linear C 10 -C 12 , and linear C 12 -C 14 alkyl dimethyl amine oxides.
- mid-branched means that the amine oxide has one alkyl moiety having n 1 carbon atoms with one alkyl branch on the alkyl moiety having n 2 carbon atoms.
- the alkyl branch is located on the ⁇ carbon from the nitrogen on the alkyl moiety.
- This type of branching for the amine oxide is also known in the art as an internal amine oxide.
- the total sum of n 1 and n 2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16.
- the number of carbon atoms for the one alkyl moiety (n 1 ) should be approximately the same number of carbon atoms as the one alkyl branch (n 2 ) such that the one alkyl moiety and the one alkyl branch are symmetric.
- symmetric means that
- the amine oxide further comprises two moieties, independently selected from a C 1-3 alkyl, a C 1-3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups.
- the two moieties are selected from a C 1-3 alkyl, more preferably both are selected as a C 1 alkyl.
- amphoteric detergent surfactants that are optional in the present invention include amido propyl betaines and derivatives of aliphatic or heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- ampholytic surfactants comprise from about 0.01% to about 20%, preferably from about 0.5% to about 10% by weight of the liquid detergent composition.
- composition used in the method of the present invention further comprises one or more alkoxylated polyethyleneimine polymer as defined in claim 1. It has been found that such an alkoxylated polyethyleneimine polymer provides an improvement in suds mileage both in soft and hard water. Therefore, when combined with the polymer of the present invention, a much stronger suds performance profile across water hardnesses is observed.
- the combination of the 2 polymers further provides excellent grease cleaning especially through the broad range of regular to baked-on grease.
- composition to be used in the method of the present invention comprises from 0.01 wt% to 10 wt%, preferably from 0.01 wt% to 2 wt%, more preferably from 0.1 wt% to 1.5 wt%, even more preferable from 0.2% to 1.5% by weight of the composition of an alkoxylated polyethyleneimine polymer.
- the alkoxylated polyethyleneimine polymer of the present composition has a polyethyleneimine backbone having from 400 to 10000 weight average molecular weight, preferably from 400 to 7000 weight average molecular weight, alternatively from 3000 to 7000 weight average molecular weight.
- polyamines can be prepared for example, by polymerizing ethyleneimine in presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid.
- a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid.
- the alkoxylation of the polyethyleneimine backbone includes: (1) one or two alkoxylation modifications per nitrogen atom, dependent on whether the modification occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom on a polyalkoxylene chain having an average of 1 to 30 alkoxy moieties per modification, wherein the terminal alkoxy moiety of the alkoxylation modification is capped with hydrogen, a C 1 -C 4 alkyl or mixtures thereof; (2) a substitution of one C 1 -C 4 alkyl moiety or benzyl moiety and one or two alkoxylation modifications per nitrogen atom, dependent on whether the substitution occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom by a polyalkoxylene chain having an average of 1 to 40 alkoxy moieties per modification wherein the terminal alk
- the alkoxylation modification of the polyethyleneimine backbone consists of the replacement of a hydrogen atom by a polyalkoxylene chain having an average of 1 to 30 alkoxy moieties, preferably from 5 to 20 alkoxy moieties.
- the alkoxy moieties are selected from ethoxy (EO), 1,2-propoxy (1,2-PO), 1,3-propoxy (1,3-PO), butoxy (BO), and combinations thereof.
- the polyalkoxylene chain is selected from ethoxy moieties and ethoxy/propoxy block moieties.
- the polyalkoxylene chain is ethoxy moieties in an average degree of from 5 to 15 and the polyalkoxylene chain is ethoxy/propoxy block moieties having an average degree of ethoxylation from 5 to 15 and an average degree of propoxylation from about 1 to 16.
- the polyalkoxylene chain is the ethoxy/propoxy block moieties wherein the propoxy moiety block is the terminal alkoxy moiety block.
- alkylating agent such as alkyl sulfates, alkyl halides, benzyl sulfates, or benzyl halides resulting in permanent quaternisation.
- the degree of permanent quaternization may be from 0% to about 30% and even 60% of the polyethyleneimine backbone nitrogen atoms. It is preferred to have less than 30% of the polyethyleneimine backbone nitrogen atoms permanently quaternized.
- a preferred modified polyethyleneimine has the general structure of formula (I): wherein the polyethyleneimine backbone has a weight average molecular weight of 600 or 5000, n of formula (I) has an average of 5-10 and R of formula (I) is selected from hydrogen, a C 1 -C 4 alkyl and mixtures thereof.
- Another preferred polyethyleneimine has the general structure of formula (II): wherein the polyethyleneimine backbone has a weight average molecular weight of either 600 or 5000, n of formula (II) has an average of 10, m of formula (II) has an average of 7 and R of formula (II) is selected from hydrogen, a C 1 -C 4 alkyl and mixtures thereof.
- the degree of permanent quaternization of formula (II) may be from 0% to about 30%, preferably to 22% of the polyethyleneimine backbone nitrogen atoms.
- PEI 5000 backbone molecular weight 5000
- EO exthoxy moieties
- NH polyethyleneiminie backbone
- PEI 5000 Polyethyleneimine (backbone molecular weight 5000) hereinafter PEI 5000 with 10 exthoxy moieties (EO) and 7 propoxy moieties (PO) per nitrogen of the polyethyleneiminie backbone (NH)
- PEI5000 polyethyleneimine (backbone molecular weight 5000) hereinafter PEI5000 with 10 exthoxy moieties (EO) and 7 propoxy moieties (PO) per nitrogen of the polyethyleneiminie backbone (NH) with 22% quaternization
- PEI600 Polyethyleneimine (backbone molecular weight 600) hereinafter PEI600 with 10 exthoxy moieties (EO) and 7 propoxy moieties (PO) per nitrogen of the polyethyleneiminie backbone (NH)
- magnesium ions may be utilized in the detergent composition when the compositions are used in softened water that contains few divalent ions.
- the magnesium ions preferably are added as a hydroxide, chloride, acetate, sulphate, formate, oxide or nitrate salt to the compositions of the present invention.
- the magnesium ions are present at an active level of from 0.01% to 1.5%, preferably from 0.015% to 1%, more preferably from 0.025 % to 0.5%, by weight of the liquid detergent composition.
- compositions may optionally comprise a solvent.
- suitable solvents include C 4-14 ethers and diethers, glycols, alkoxylated glycols, C 6 -C 16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C 1 -C 5 alcohols, linear C 1 -C 5 alcohols, amines, C 8 -C 14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
- the liquid detergent composition When present, the liquid detergent composition will contain from 0.01% to 20%, preferably from 0.5% to 20%, more preferably from 1% to 10% by weight of the liquid detergent composition of a solvent.
- solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.
- the liquid detergent compositions of the invention may optionally comprise a hydrotrope in an effective amount so that the liquid detergent compositions are appropriately compatible in water.
- Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulphonate, sodium, potassium and ammonium toluene sulphonate, sodium potassium and ammonium cumene sulphonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903 .
- the liquid detergent compositions of the present invention typically comprise from 0% to 15% by weight of the liquid detergent composition of a hydrotropic, or mixtures thereof, preferably from 1% to 10%, most preferably from 3% to 6% by weight.
- compositions of the present invention may optionally contain a polymeric suds stabilizer.
- These polymeric suds stabilizers provide extended suds volume and suds duration of the liquid detergent compositions.
- These polymeric suds stabilizers may be selected from homopolymers of (N,N-dialkylamino) alkyl esters and (N,N-dialkylamino) alkyl acrylate esters.
- the weight average molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from 1,000 to 2,000,000, preferably from 5,000 to 1,000,000, more preferably from 10,000 to 750,000, more preferably from 20,000 to 500,000, even more preferably from 35,000 to 200,000.
- the polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulphate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
- a salt either an inorganic or organic salt, for example the citrate, sulphate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
- One preferred polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate esters, namely the acrylate ester represented by the formula (VII):
- the polymeric suds booster may be present in the composition from 0.01% to 15%, preferably from 0.05% to 10%, more preferably from 0.1% to 5%, by weight of the liquid detergent composition.
- compositions according to the present invention is a diamine. Since the habits and practices of the users of liquid detergent compositions show considerable variation, the composition will preferably contain 0% to 15%, preferably 0.1% to 15%, preferably 0.2% to 10%, more preferably 0.25% to 6%, more preferably 0.5% to 1.5% by weight of said composition of at least one diamine.
- Preferred organic diamines are those in which pK1 and pK2 are in the range of 8.0 to 11.5, preferably in the range of 8.4 to 11, even more preferably from 8.6 to 10.75.
- pKa1 and pKa2 are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from " Critical Stability Constants: Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London, 1975 .
- pKa's can be obtained from relevant company literature, such as information supplied by DUPONT®, a supplier of diamines.
- relevant company literature such as information supplied by DUPONT®, a supplier of diamines.
- the pKa of the diamines is specified in an all-aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M.
- the liquid detergent compositions according to the present invention may comprise a linear or cyclic carboxylic acid or salt thereof to improve the rinse feel of the composition.
- Carboxylic acids useful herein include C 1-6 linear or at least 3 carbon containing cyclic acids.
- the linear or cyclic carbon-containing chain of the carboxylic acid or salt thereof may be substituted with a substituent group selected from the group consisting of hydroxyl, ester, ether, aliphatic groups having from 1 to 6, more preferably 1 to 4 carbon atoms, and mixtures thereof.
- Preferred carboxylic acids are those selected from the group consisting of salicylic acid, maleic acid, acetyl salicylic acid, 3 methyl salicylic acid, 4 hydroxy isophthalic acid, dihydroxyfumaric acid, 1,2, 4 benzene tricarboxylic acid, pentanoic acid and salts thereof and mixtures thereof.
- the carboxylic acid exists in the salt form, the cation of the salt is preferably selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.
- the carboxylic acid or salt thereof when present, is preferably present at the level of from 0.1% to 5%, more preferably from 0.2% to 1% and most preferably from 0.25% to 0.5%.
- the liquid detergent compositions herein are formulated as clear liquid compositions.
- clear it is meant stable and transparent.
- the use of solvents and hydrotropes is well known to those familiar with the art of light-duty liquid dishwashing compositions.
- Preferred liquid detergent compositions in accordance with the invention are clear single phase liquids, but the invention also embraces clear and opaque products containing dispersed phases, such as beads or pearls as described in US 5,866,529, to Erilli, et al. , and US 6,380,150, to Toussaint, et al. , provided that such products are physically stable (i.e., do not separate) on storage.
- the liquid detergent compositions of the present invention may be packages in any suitable packaging for delivering the liquid detergent composition for use.
- the package is a clear package made of glass or plastic.
- liquid detergent compositions herein can further comprise a number of other optional ingredients suitable for use in liquid detergent compositions such as perfume, dyes, opacifiers, enzymes, chelants, thickening agents and pH buffering means so that the liquid detergent compositions herein generally have a pH of from 4 to 14, preferably 6 to 13, most preferably 6 to 10.
- other optional ingredients suitable for use in liquid detergent compositions such as perfume, dyes, opacifiers, enzymes, chelants, thickening agents and pH buffering means so that the liquid detergent compositions herein generally have a pH of from 4 to 14, preferably 6 to 13, most preferably 6 to 10.
- the viscosity of the composition of the present invention is measured on a Brookfield viscometer model # LVDVII+ at 20 °C.
- the spindle used for these measurements is S31 with the appropriate speed to measure products of different viscosities; e.g., 12rpm to measure products of viscosity greater than 1000cps; 30 rpm to measure products with viscosities between 500cps - 1000 cps; 60 rpm to measure products with viscosities less than 500cps.
- Nonionic may be either C 11 Alkyl ethoxylated surfactant containing 9 ethoxy groups or C10 alkly ethoxylated surfactant containing 8 ethoxy groups.
- the following 6 amphiphilic graft polymers may be prepared as follows.
- the K values may be measured in 3% by weight aqueous NaCl solution at 23°C and a polymer concentration of 1% by weight.
- the mean molar masses and polydispersities are determined by gel permeation chromatography using a 0.5% by weight LiBr solution in dimethylacetamide as the eluent and of polymethyl methacrylate (PMMA) as the standard.
- the degrees of branching may be determined by 13 C NMR spectroscopy in deuterated dimethyl sulfoxide from the integrals of the signals of the graft sites and the -CH 2 -groups of the polyethylene glycol.
- the values reported relate to all of the polyethylene glycol present in the product, i.e. including ungrafted polyethylene glycol, and correspond to the number of side chains present on average per polyethylene glycol.
- a polymerization vessel equipped with stirrer and reflux condenser is initially charged with 480 g of polyethylene glycol (M n 12,000) under a nitrogen atmosphere and melted at 70°C.
- the resulting graft polymer has a K value of 28.4, a polydispersity of 1.8 (weight average molecular weight, M w , 36,900, and number average molecular weight, M n , 21,000) and a degree of branching of 0.8% (corresponds to 0.15 graft site/50 EO units).
- a polymerization vessel equipped with stirrer and reflux condenser is initially charged with 400 g of polyethylene glycol (M n 9000) under a nitrogen atmosphere and melted at 85°C.
- the resulting graft polymer has a K value of 24.0, a polydispersity of 1.9 (M w 37 000, M n 19 500) and a degree of branching of 0.8% (corresponds to 0.20 graft site/50 EO units).
- a polymerization pressure vessel equipped with stirrer and reflux condenser is initially charged with 1000 g of polyethylene glycol (M n 6000) under a nitrogen atmosphere and melted at 90°C. Then, 1500 g of vinyl acetate within 6 h (feed 1) and 14.5 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 60.5 g of tripropylene glycol, within 7 h (feed 2) are metered in parallel continuously with constant flow rates at internal temperature 90°C with stirring.
- M n 6000 polyethylene glycol
- the resulting graft polymer has a K value of 19.6, a polydispersity of 1.9 (M w 35,700, M n 18,800) and a degree of branching of 0.9% (corresponds to 0.33 graft site/50 EO units).
- a polymerization vessel equipped with stirrer and reflux condenser is initially charged with 480 g of polyethylene glycol (M n 12,000) under a nitrogen atmosphere and melted at 70°C.
- the resulting graft polymer has a K value of 29.1, a polydispersity of 1.9 (M w 35,500, M n 18,400) and a degree of branching of 0.7% (corresponds to 0.13 graft site/50 EO units).
- a polymerization pressure vessel equipped with stirrer and reflux condenser is initially charged with 1175 g of polyethylene glycol (M n 4000) under a nitrogen atmosphere and melted at 90°C.
- the resulting graft polymer has a K value of 17.9, a polydispersity of 2.3 (M w 26,800, M n 11,700) and a degree of branching of 0.6% (corresponds to 0.33 graft site/50 EO units).
- a polymerization pressure vessel equipped with stirrer and reflux condenser is initially charged with 444 g of polyethylene glycol (M n 6000) under a nitrogen atmosphere and melted at 90°C.
- Residue amounts of vinyl acetate are removed by vacuum distillation at 90°C. Subsequently, a solids content of 86.9% by weight is established by adding water.
- the resulting graft polymer has K value of 17.6, a polydispersity of 1.8 (M w 35,700, M n 20,000) and a degree of branching of 0.9% (corresponds to 0.33 graft site/50 EO units).
Abstract
Description
- The present invention relates to a method of cleaning dishware with a liquid detergent composition comprising an amphiphilic graft polymer to provide improved baked-on grease cleaning from dish surfaces and improved suds profile.
- Grease cleaning with liquid detergents poses an ongoing problem for consumers. Consumers utilizing liquid detergent as a light-duty liquid dishwashing detergent composition tend to wash greasy, difficult to clean items at the end of their washing experience, after easier to clean items such as glasses and flatware are cleaned. Light-duty liquid dishwashing detergent compositions require a high suds profile while providing grease cleaning.
- It has been surprisingly found that the method of the present invention is highly efficient in removing grease and in particular the more difficult baked-on grease layer. Without wishing to be bound by theory, it is believed that this baked-on grease is characterized by a higher hydrophobicity. The removal of such baked-on grease therefore requires surfactants with strong hydrophobic properties in order to penetrate and fluidify efficiently the grease layer and/or requires very high level of total surfactants.
- However, the use of significant levels of such highly hydrophobic surfactants presents the disadvantages of acting as soil itself and hence of monopolizing the other surfactants of the composition. Thereby, it reduces the efficiency of the composition on the basic regular grease cleaning. It has also been found that the introduction of significant levels of hydrophobic surfactants cause phase instability and suds suppression, which limits their use in dishwashing compositions.
- It has been found further that the alternative route of extreme high levels of total surfactant cause phase stability issues, even if the presence of hydrophobic surfactants is minimized. High levels of total surfactant are typically found in more concentrated dishwashing liquids. It has been found that the addition of the amphiphilic graft polymer of the present invention allows that total surfactant level to be maintained or even reduced whilst still maintaining or even improving grease performance.
- Furthermore, it has been found that the amphiphilic graft polymer of the present invention improves the suds profile of the light-duty liquid dishwashing detergent composition to be used in the method of the present invention. It increases suds mileage, especially in soft water.
- Therefore, the present invention teaches a method of washing dishes with a liquid detergent composition comprising a specific amphiphilic graft polymer.
- The present application relates to a method of cleaning dishware with a liquid detergent composition comprising an amphiphilic grafted polymer and an alkoxylated polyethyleneimine polymer according to claim 1.
- The method of cleaning dishware of the present invention surprisingly provides improved grease cleaning, especially on baked-on grease while maintaining acceptable levels of total amount of such cleaning and improved suds profile in a liquid dishwashing detergent composition.
- As used herein "grease" means materials comprising at least in part (i.e., at least 0.5 wt% by weight of the grease) saturated and unsaturated fats and oils, preferably oils and fats derived from animal sources such as beef and/or chicken.
- As used herein "baked-on grease" means materials comprising grease exposed to increased temperatures in a standard oven, convection oven, toaster oven, microwave oven, stove top heating using a frying pan, wok, hot plate, electric griddle, or other known cooking appliances used to heat food during cooking.
- As used herein "suds profile" means amount of sudsing (high or low) and the persistence of sudsing (sustained or prevention) throughout the washing process resulting from the use of the liquid detergent composition of the present composition. Liquid dishwashing detergent compositions require high sudsing and sustained suds. This is particularly important with respect to liquid dishwashing detergent compositions as the consumer uses high sudsing as an indicator of the performance of the detergent composition. Moreover, the consumer in a liquid dishwashing detergent composition also uses the sudsing profile as an indicator that the wash solution still contains active detergent ingredients. The consumer usually renews the wash solution when the sudsing subsides. Thus, a low sudsing liquid dishwashing detergent composition formulation will tend to be replaced by the consumer more frequently than is necessary because of the low sudsing level.
- As used herein "dishware" means a surface such as dishes, glasses, pots, pans, baking dishes and flatware made from ceramic, china, metal, glass, plastic (polyethylene, polypropylene, polystyrene, etc.) and wood.
- As used herein "light-duty liquid dishwashing detergent composition" refers to those compositions that are employed in manual (i.e. hand) dishwashing. Such compositions are generally high sudsing or foaming in nature.
- As used herein "cleaning" means applying to a surface for the purpose of cleaning, and/or disinfecting.
- The present invention is directed to a process of cleaning a dishware with a light duty liquid composition comprising the amphiphilic graft polymer and alkoxylated polyethyleneimine according to claim 1. Said process comprises the steps of applying said composition onto said dishware, typically in diluted or neat form and rinsing or leaving said composition to dry on said surface without rinsing said surface.
- By "in its neat form", it is meant herein that said liquid composition is applied directly onto the surface to be treated without undergoing any dilution by the user (immediately) prior to the application. By "diluted form", it is meant herein that said liquid composition is diluted by the user with an appropriate solvent, typically with water. By "rinsing", it is meant herein contacting the dishware cleaned with the process according to the present invention with substantial quantities of appropriate solvent, typically water, after the step of applying the liquid composition herein onto said dishware. By "substantial quantities", it is meant usually 5 to 20 liters.
- In one embodiment of the present invention, the composition herein can be applied in its diluted form. Soiled dishes are contacted with an effective amount, typically from 0.5 ml to 20 ml (per 25 dishes being treated), preferably from 3ml to 10 ml, of the liquid detergent composition of the present invention diluted in water. The actual amount of liquid detergent composition used will be based on the judgment of user, and will typically depend upon factors such as the particular product formulation of the composition, including the concentration of active ingredients in the composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like. The particular product formulation, in turn, will depend upon a number of factors, such as the intended market (i.e., U.S., Europe, Japan, etc.) for the composition product. Suitable examples may be seen below in Table A.
- Generally, from 0.01 ml to 150 ml, preferably from 3ml to 40ml of a liquid detergent composition of the invention is combined with from 2000 ml to 20000 ml, more typically from 5000 ml to 15000 ml of water in a sink having a volumetric capacity in the range of from 1000 ml to 20000 ml, more typically from 5000 ml to 15000 ml. The soiled dishes are immersed in the sink containing the diluted compositions then obtained, where contacting the soiled surface of the dish with a cloth, sponge, or similar article cleans them. The cloth, sponge, or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface, and is typically contacted with the dish surface for a period of time ranged from 1 to 10 seconds, although the actual time will vary with each application and user. The contacting of cloth, sponge, or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
- Another method of the present invention will comprise immersing the soiled dishes into a water bath or held under running water without any liquid dishwashing detergent. A device for absorbing liquid dishwashing detergent, such as a sponge, is placed directly into a separate quantity of undiluted liquid dishwashing composition for a period of time typically ranging from 1 to 5 seconds. The absorbing device, and consequently the undiluted liquid dishwashing composition, is then contacted individually to the surface of each of the soiled dishes to remove said soiling. The absorbing device is typically contacted with each dish surface for a period of time range from 1 to 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish. The contacting of the absorbing device to the dish surface is preferably accompanied by concurrent scrubbing.
- The composition used in the method according to the present invention is formulated as a liquid light-duty liquid dishwashing detergent composition comprising an amphiphilic graft polymer and alkoxylated polyethyleneimine polymer.
- The amphiphilic graft polymer will typically be present in the composition of the present invention at a level of from 0.01 wt% to 5.0 wt%, preferably from 0.1 wt% to 2.0 wt%, more preferably from 0.2% to 1.5% by weight of the composition.
- (i) The polymer herein is a random graft copolymer having a hydrophilic backbone and hydrophobic side chains. Typically, the hydrophilic backbone is less than about 70%, less than about 50%, or from about 50% to about 2%, or from about 45% to about 5%, or from about 40% to about 10% by weight of the polymer. The backbone contains monomers selected from the group consisting of unsaturated C2-6 acid, ether, alcohol, aldehyde, ketone or ester, sugar unit, alkoxy unit, maleic anhydride and saturated polyalcohol such as glycerol, and a mixture thereof The hydrophilic backbone may contain acrylic acid, methacrylic acid, maleic acid, vinyl acetic acid, glucoside, alkylene oxide, glycerol, or a mixture thereof. The polymer may contain either a linear or branched polyalkylene oxide backbone with ethylene oxide, propylene oxide and/or butylene oxide. The polyalkylene oxide backbone may contain more than about 80%, or from about 80% to about 100%, or from about 90% to about 100% or from about 95% to about 100% by weight ethylene oxide. The weight average molecular weight (Mw) of the polyalkylene oxide backbone is typically from about 400 g/mol to 40,000 g/mol, or from about 1,000 g/mol to about 18,000 g/mol, or from about 3,000 g/mol to about 13,500 g/mol, or from about 4,000 g/mol to about 9,000 g/mol. The polyalkylene backbone may be extended by condensation with suitable connecting molecules, such as dicarboxylic acids and/or diisocianates.
The backbone contains a plurality of hydrophobic side chains attached thereto, selected from C4-25 alkyl group; polypropylene; polybutylene; a vinyl ester of a saturated monocarboxylic C1-6 acid; and/or a C1-6 alkyl ester of acrylic or methacrylic acid, and a mixture thereof. The hydrophobic side chains may contain, by weight of the hydrophobic side chains, at least about 50% vinyl acetate, or from about 50% to about 100% vinyl acetate, or from about 70% to about 100% vinyl acetate, or from about 90% to about 100% vinyl acetate. The hydrophobic side chains may contain, by weight of the hydrophobic side chains, from about 70% to about 99.9% vinyl acetate, or from about 90% to about 99% vinyl acetate. The hydrophobic side chains may also contain, by weight of the hydrophobic side chains, from about 0.1% to about 10 % butyl acrylate, or from about 1% to about 7% butyl acrylate, or from about 2% to about 5% butyl acrylate. The hydrophobic side chains may also contain a modifying monomer, such as styrene, N-vinylpyrrolidone, acrylic acid, methacrylic acid, maleic acid, acrylamide, vinyl acetic acid and/or vinyl formamide, especially styrene and/or N-vinylpyrrolidone, at levels of from about 0.1% to about 10%, or from about 0.1% to about 5%, or from about 0.5% to about 6%, or from about 0.5% to about 4%, or from about 1% to about 3%, by weight of the hydrophobic side chains.
The polymer may be formed by grafting (a) polyethylene oxide; (b) a vinyl ester from acetic acid and/or propionic acid; and/or a C1-4 alkyl ester of acrylic or methacrylic acid; and (c) modifying monomers. The polymer may have the general formula: - (ii) Preferred graft polymers for the present invention are amphiphilic graft polymers based on water-soluble polyalkylene oxides (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), said polymers having an average of three, preferably one graft site per 50 alkylene oxide units and mean molar masses Mw of from 3000 to 100 000.
A material within this definition, based on polyethylene oxide of molecular weight 6000 (equivalent to 136 ethylene oxide units), containing approximately 3 parts by weight of vinyl acetate units per 1 part by weight of polyethylene oxide, and having itself a molecular weight of 24 000, is commercially available from BASF as Sokalan (Trade Mark) HP22.
These graft polymers can be prepared by polymerizing a vinyl ester component (B) composed of vinyl acetate and/or vinyl propionate (B1) and, if desired, a further ethylenically unsaturated monomer (B2), in the presence of a water-soluble polyalkylene oxide (A), a free radical-forming initiator (C) and, if desired, up to 40% by weight, based on the sum of components (A), (B) and (C), of an organic solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomer (B) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polyalkylene oxide (A).
The graft polymers are characterized by their low degree of branching (degree of grafting). They have, on average, based on the reaction mixture obtained, not more than 1 graft site, preferably not more than 0.6 graft site, more preferably not more than 0.5 graft site and most preferably not more than 0.4 graft site per 50 alkylene oxide units. They comprise, on average, based on the reaction mixture obtained, preferably at least 0.05, in particular at least 0.1 graft site per 50 alkylene oxide units. The degree of branching can be determined, for example, by means of 13C NMR spectroscopy from the integrals of the signals of the graft sites and the -CH2-groups of the polyalkylene oxide.
In accordance with their low degree of branching, the molar ratio of grafted to ungrafted alkylene oxide units in the inventive graft polymers is from 0.002 to 0.05, preferably from 0.002 to 0.035, more preferably from 0.003 to 0.025 and most preferably from 0.004 to 0.02. - (iii) More preferably, the graft polymers feature a narrow molar mass distribution and hence a polydispersity Mw/Mn of generally 3, preferably 2.5 and more preferably 2.3. Most preferably, their polydispersity Mw/Mn is in the range from 1.5 to 2.2. The polydispersity of the graft polymers can be determined, for example, by gel permeation chromatography using narrow-distribution polymethyl methacrylates as the standard.
- The mean molecular weight Mw of the graft polymers is from 3000 to 100 000, preferably from 6000 to 45 000 and more preferably from 8000 to 30 000.
- Owing to their low degree of branching and their low polydispersity, the amphiphilic character and the block polymer structure of the graft polymers is particularly marked.
- The graft polymers also have only a low content of ungrafted polyvinyl ester (B). In general, they comprise 10% by weight, preferably 7.5% by weight and more preferably 5% by weight of ungrafted polyvinyl ester (B).
- Owing to the low content of ungrafted polyvinyl ester and the balanced ratio of components (A) and (B), the graft polymers are soluble in water or in water/alcohol mixtures (for example a 25% by weight solution of diethylene glycol monobutyl ether in water). They have pronounced, low cloud points which, for the graft polymers soluble in water at up to 50°C, are generally 95°C, preferably 85°C and more preferably 75°C, and, for the other graft polymers in 25% by weight diethylene glycol monobutyl ether, generally 90°C, preferably from 45 to 85°C.
- The amphiphilic graft polymers have preferably (A) from 20% to 70% by weight of a water-soluble polyalkylene oxide as a graft base and (B) side chains formed by free-radical polymerization of from 30% to 80% by weight of a vinyl ester component composed of
- (B1) from 70% to 100% by weight of vinyl acetate and/or vinyl propionate and
- (B2) from 0 to 30% by weight of a further ethylenically unsaturated monomer, in the presence of (A).
- More preferably, they comprise from 25% to 60% by weight of the graft base (A) and from 40% to 75% by weight of the polyvinyl ester component (B).
- Water-soluble polyalkylene oxides suitable for forming the graft base (A) are in principle all polymers based on C2-C4-alkylene oxides which comprise at least 50% by weight, preferably at least 60% by weight, more preferably at least 75% by weight of ethylene oxide in copolymerized form.
- The polyalkylene oxides (A) preferably have a low polydispersity Mw/Mn. Their polydispersity is preferably 1.5.
- The polyalkylene oxides (A) may be the corresponding polyalkylene glycols in free form, i.e. with OH end groups, but they may also be capped at one or both end groups. Suitable end groups are, for example, C1-C25-alkyl, phenyl and C1-C14-alkylphenyl groups.
- Specific examples of particularly suitable polyalkylene oxides (A) include:
- (A1) polyethylene glycols which may be capped at one or both end groups, especially by C1-C25-alkyl groups, but are preferably not etherified, and have mean molar masses Mn of preferably from 1500 to 20 000, more preferably from 2500 to 15 000;
- (A2) copolymers of ethylene oxide and propylene oxide and/or butylene oxide with an ethylene oxide content of at least 50% by weight, which may likewise be capped at one or both end groups, especially by C1-C25-alkyl groups, but are preferably not etherified, and have mean molar masses Mn of preferably from 1500 to 20 000, more preferably from 2500 to 15 000;
- (A3) chain-extended products having mean molar masses of in particular from 2500 to 20 000, which are obtainable by reacting polyethylene glycols (A1) having mean molar masses Mn of from 200 to 5000 or copolymers (A2) having mean molar masses Mn of from 200 to 5000 with C2-C12-dicarboxylic acids or -dicarboxylic esters or C6-C18-diisocyanates.
- Preferred graft bases (A) are the polyethylene glycols (A1).
- The side chains of the graft polymers are formed by polymerization of a vinyl ester component (B) in the presence of the graft base (A).
- The vinyl ester component (B) may consist advantageously of (B1) vinyl acetate or vinyl propionate or of mixtures of vinyl acetate and vinyl propionate, particular preference being given to vinyl acetate as the vinyl ester component (B).
- However, the side chains of the graft polymer can also be formed by copolymerizing vinyl acetate and/or vinyl propionate (B1) and a further ethylenically unsaturated monomer (B2). The fraction of monomer (B2) in the vinyl ester component (B) may be up to 30% by weight, which corresponds to a content in the graft polymer of (B2) of 24% by weight.
- Suitable comonomers (B2) are, for example, monoethylenically unsaturated carboxylic acids and dicarboxylic acids and their derivatives, such as esters, amides and anhydrides, and styrene. It is of course also possible to use mixtures of different comonomers.
- Specific examples include: (meth)acrylic acid, C1-C12-alkyl and hydroxy-C2-C12-alkyl esters of (meth)acrylic acid, (meth)acrylamide, N-C1-C12-alkyl(meth)acrylamide, N,N-di(C1-C6-alkyl)(meth)acrylamide, maleic acid, maleic anhydride and mono(C1-C12-alkyl)esters of maleic acid.
- Preferred monomers (B2) are the C1-C8-alkyl esters of (meth)acrylic acid and hydroxyethyl acrylate, particular preference being given to the C1-C4-alkyl esters of (meth)acrylic acid.
- Very particularly preferred monomers (B2) are methyl acrylate, ethyl acrylate and in particular n-butyl acrylate.
- When the graft polymers comprise the monomers (B2) as a constituent of the vinyl ester component (B), the content of graft polymers in (B2) is preferably from 0.5% to 20% by weight, more preferably from 1% to 15% by weight and most preferably from 2% to 10% by weight.
- The graft polymers are advantageously obtainable by polymerizing a vinyl ester component (B) composed of vinyl acetate and/or vinyl propionate (B1) and, if desired, a further ethylenically unsaturated monomer (B2), in the presence of a water-soluble polyalkylene oxide (A), a free radical-forming initiator (C) and, if desired, up to 40% by weight, based on the sum of components (A), (B) and (C), of an organic solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomer (B) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polyalkylene oxide (A).
- In this process, preference is given to using from 30% to 80% by weight of a vinyl ester component (B) composed of (B1) from 70% to 100% by weight of vinyl acetate and/or vinyl propionate and (B2) from 0 to 30% by weight of a further ethylenically unsaturated monomer and from 20% to 70% by weight of a water-soluble polyalkylene oxide (A) of mean molar mass Mn of from 1500 to 20 000.
- The amount of initiator (C) is preferably from 0.2% to 5% by weight, in particular from 0.5% to 3.5% by weight, based in each case on component (B).
- For the process, it is essential that the steady-state concentration of radicals present at the mean polymerization temperature is substantially constant and the graft monomer (B) is present in the reaction mixture constantly only in low concentration (for example of not more than 5% by weight). This allows the reaction to be controlled, and graft polymers can be prepared in a controlled manner with the desired low degree of branching and the desired low polydispersity.
- The term "mean polymerization temperature" is intended to mean here that, although the process is substantially isothermal, there may, owing to the exothermicity of the reaction, be temperature variations which are preferably kept within the range of+/- 10°C, more preferably in the range of +/- 5°C.
- The free radical-forming initiator (C) at the mean polymerization temperature should have a decomposition half-life of from 40 to 500 min, preferably from 50 to 400 min and more preferably from 60 to 300 min.
- The initiator (C) and the graft monomer (B) are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and graft monomer (B) is present in the reaction mixture. The proportion of undecomposed initiator in the overall reaction mixture is preferably ≤ 15% by weight, in particular ≤ 10% by weight, based on the total amount of initiator metered in during the monomer addition.
- The mean polymerization temperature is appropriately in the range from 50°C to 140°C, preferably from 60°C to 120°C and more preferably from 65°C to 110°C.
- Examples of suitable initiators (C) whose decomposition half-life in the temperature range from 50°C to 140°C is from 20 to 500 min are:
- O-C2-C12-acylated derivatives of tert-C4-C12-alkyl hydroperoxides and tert-(C9-C12-aralkyl) hydroperoxides, such as tert-butyl peroxyacetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhcxanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyneodecanoate, 1, 1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate and di-tert-butyl diperoxyphthalate;
- di-O-C4-C12-acylated derivatives of tert-C8-C14-alkylene bisperoxides, such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene;
- di(C2-C12-alkanoyl) and dibenzoyl peroxides, such as diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dicapryloyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide and di(2,4-dichlorobenzoyl) peroxide;
- tert-C4-C5-alkyl peroxy(C4-C12-alkyl)carbonates, such as tert-amyl peroxy(2-ethylhexyl)carbonate;
- di(C2-C12-alkyl) peroxydicarbonates, such as di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.
- Depending on the mean polymerization temperature, examples of particularly suitable initiators (C) are:
- at a mean polymerization temperature of from 50°C to 60°C:
- tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-di(2-neodecanoyl peroxyisopropyl)benzene, di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate;
- at a mean polymerization temperature of from 60°C to 70°C:
- tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl) peroxide;
- at a mean polymerization temperature of from 70°C to 80°C:
- tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl) peroxide and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane;
- at a mean polymerization temperature of from 80°C to 90°C:
- tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dibenzoyl peroxide and di(4-methylbenzoyl) peroxide;
- at a mean polymerization temperature of from 90°C to 100°C:
- tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide and di(4-methylbenzoyl) peroxide;
- at a mean polymerization temperature of from 100°C to 110°C:
- tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl)carbonate;
- at a mean polymerization temperature of from 110°C to 120°C:
- tert-butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl)carbonate.
- Preferred initiators (C) are O-C4-C12-acylated derivatives of tert-C4-C5-alkyl hydroperoxides, particular preference being given to tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.
- Particularly advantageous polymerization conditions can be established effortlessly by precise adjustment of initiator (C) and polymerization temperature. For instance, the preferred mean polymerization temperature in the case of use of tert-butyl peroxypivalate is from 60°C to 80°C, and, in the case oftert-butyl peroxy-2-ethylhexanoate, from 80°C to 100°C.
- The inventive polymerization reaction can be carried out in the presence of small amounts of an organic solvent (D). It is of course also possible to use mixtures of different solvents (D). Preference is given to using water-soluble or water-miscible solvents.
- When a solvent (D) is used as a diluent, generally from 1% to 40% by weight, preferably from 1% to 35% by weight, more preferably from 1.5% to 30% by weight, most preferably from 2% to 25% by weight, based in each case on the sum of the components (A), (B) and (C), are used.
- Examples of suitable solvents (D) include:
- monohydric alcohols, preferably aliphatic C1-C16-alcohols, more preferably aliphatic C2-C12-alcohols, most preferably C2-C4-alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol;
- polyhydric alcohols, preferably C2-C10-diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene glycols, such as ethylene glycol and propylene glycol;
- alkylene glycol ethers, preferably alkylene glycol mono(C1-C12-alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers, such as ethylene glycol monomethyl and -ethyl ether and propylene glycol monomethyl and -ethyl ether;
- polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2-20 C2-C4-alkylene glycol units, more preferably polyethylene glycols having 2-20 ethylene glycol units and polypropylene glycols having 2-10 propylene glycol units, most preferably polyethylene glycols having 2-15 ethylene glycol units and polypropylene glycols having 2-4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol;
- polyalkylene glycol monoethers, preferably poly(C2-C4-alkylene) glycol mono(C1-C25-alkyl) ethers having 2-20 alkylene glycol units, more preferably poly(C2-C4-alkylene) glycol mono(C1-C20-alkyl) ethers having 2-20 alkylene glycol units, most preferably poly(C2-C3-alkylene) glycol mono(C1-C16-alkyl) ethers having 3-20 alkylene glycol units;
- carboxylic esters, preferably C1-C8-alkyl esters of C1-C6-carboxylic acids, more preferably C1-C4-alkyl esters of C1-C3-carboxylic acids, most preferably C2-C4-alkyl esters of C2-C3-carboxylic acids, such as ethyl acetate and ethyl propionate;
- aliphatic ketones which preferably have from 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone;
- cyclic ethers, in particular tetrahydrofuran and dioxane.
- The solvents (D) are advantageously those solvents which are also used to formulate the inventive graft polymers for use (for example in washing and cleaning compositions) and can therefore remain in the polymerization product.
- Preferred examples of these solvents are polyethylene glycols having 2-15 ethylene glycol units, polypropylene glycols having 2-6 propylene glycol units and in particular alkoxylation products of C6-C8-alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).
- Particular preference is given here to alkoxylation products of C8-C16-alcohols with a high degree of branching, which allow the formulation of polymer mixtures which are free-flowing at 40-70°C and have a very low polymer content at comparatively low viscosity. The branching may be present in the alkyl chain of the alcohol and/or in the polyalkoxylate moiety (copolymerization of at least one propylene oxide, butylene oxide or isobutylene oxide unit). Particularly suitable examples of these alkoxylation products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide, C13/C15 oxo alcohol or C12/C14 or C16/C18 fatty alcohol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide, preference being given to 2-propylheptanol alkoxylated with 1-15 mol of ethylene oxide and 1-3 mol of propylene oxide.
- In the process, polyalkylene oxide (A), graft monomer (B1) and, if appropriate, (B2), initiator (C) and, if appropriate, solvent (D) are heated to the selected mean polymerization temperature in a reactor.
- The polymerization is carried out in such a way that an excess of polymer (polyalkylene oxide (A) and formed graft polymer) is constantly present in the reactor. The quantitative ratio of polymer to ungrafted monomer and initiator is generally ≥ 10:1, preferably ≥ 15:1 and more preferably ≥ 20:1.
- The polymerization process according to the invention can in principle be carried out in various reactor types.
- The reactor used is preferably a stirred tank in which the polyalkylene oxide (A), if appropriate together with portions, of generally up to 15% by weight of the particular total amount, of graft monomers (B), initiator (C) and solvent (D), are initially charged fully or partly and heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are metered in, preferably separately. The remaining amounts of (B), (C) and, if appropriate, (D) are metered in preferably over a period of ≥ 2 h, more preferably of ≥ 4 h and most preferably of≥ 5 h.
- In the case of the particularly preferred, substantially solvent-free process variant, the entire amount of polyalkylene oxide (A) is initially charged as a melt and the graft monomers (B1) and, if appropriate, (B2), and also the initiator (C) present preferably in the form of a from 10 to 50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled such that the selected polymerization temperature, on average during the polymerization, is maintained with a range of especially +/- 10°C, in particular +/- 5°C.
- In a further particularly preferred, low-solvent process variant, the procedure is as described above, except that solvent (D) is metered in during the polymerization in order to limit the viscosity of the reaction mixture. It is also possible to commence with the metered addition of the solvent only at a later time with advanced polymerization, or to add it in portions.
- The polymerization can be effected under standard pressure or at reduced or elevated pressure. When the boiling point of the monomers (B) or of any diluent (D) used is exceeded at the selected pressure, the polymerization is carried out with reflux cooling.
- The liquid detergent compositions herein further contain from 30% to 80% of an aqueous liquid carrier in which the other essential and optional compositions components are dissolved, dispersed or suspended. More preferably the aqueous liquid carrier will comprise from 45% to 70%, more preferable from 45% to 65% of the compositions herein.
- One preferred component of the aqueous liquid carrier is water. The aqueous liquid carrier, however, may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (20°C - 25°C) and which may also serve some other function besides that of an inert filler. Such materials can include, for example, hydrotropes and solvents, discussed in more detail below. Dependent on the geography of use of the liquid detergent composition of the present invention, the water in the aqueous liquid carrier can have a hardness level of about 2-30 gpg ("gpg" is a measure of water hardness that is well known to those skilled in the art, and it stands for "grains per gallon").
- The liquid detergent composition may have any suitable pH. Preferably the pH of the composition is adjusted to between 4 and 14. More preferably the composition has pH of between 6 and 13, most preferably between 6 and 10. The pH of the composition can be adjusted using pH modifying ingredients known in the art.
- The liquid detergent compositions of the present invention are preferably thickened and have viscosity of greater than 500 cps, when measured at 20°C. More preferably the viscosity of the composition is between 500 and 1100 cps.
- A preferred further ingredient of the hand dishwashing composition of the present invention is a surfactant selected from nonionic, anionic, cationic surfactants, ampholytic, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof. Surfactants can be comprised at a level of from 1.0% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 25% to 40% by weight preferably from 30% to 38% by weight of the liquid detergent composition. Non-limiting examples of optional surfactants are discussed below.
- High levels of surfactants, in particular high levels of anionic surfactants and/or hydrophobic surfactants, which may be desired for high grease cleaning performance, especially on more hydrophobic greases, cause instability of the dishwashing compositions. High levels of hydrophobic surfactants furthermore cause also suds suppression.
- It has been found that the amphiphilic graft polymer of the present invention is highly effective in producing highly effective grease cleaning, especially on more hydrophobic greases, without having to resort to extreme levels (eg above 35-40%) of total surfactant, and/or extreme levels of hydrophilic (C12-C14 chain) anionic surfactant (eg above 25-30%) and/or high levels (eg above 5%) of hydrophobic surfactants (NI surfactants and/or >14C chain anionic surfactants). Indeed, the addition of the amphiphilic graft polymer of the present invention allows to obtain the same or even better grease cleaning and sudsing performances without the addition of high levels of these surfactants.
- In a preferred embodiment, the composition to be used in the method of the present invention will comprise an anionic surfactant. Preferred anionic surfactants are the sulphate and surlfonate surfactants, more preferred are the alkyl sulphonates and paraffin sulphonates, even more preferred is linear alkyl sulphonate.
- The sulphate or sulphonate surfactant is typically present at a level of at least 5%, preferably from 5% to 40% and more preferably from 15% to 30% and even more preferably at 15% to 25% by weight of the liquid detergent composition.
- Suitable sulphate or sulphonate surfactants for use in the compositions herein include water-soluble salts or acids of C10-C14 alkyl or hydroxyalkyl, sulphate or sulphonates. Suitable counterions include hydrogen, alkali metal cation or ammonium or substituted ammonium, but preferably sodium.
- Where the hydrocarbyl chain is branched, it preferably comprises C1-4 alkyl branching units. The average percentage branching of the sulphate or sulphonate surfactant is preferably greater than 30%, more preferably from 35% to 80% and most preferably from 40% to 60% of the total hydrocarbyl chains.
The sulphate or sulphonate surfactants may be selected from C11-C18 alkyl benzene sulphonates (LAS), C8-C20 primary, branched-chain and random alkyl sulphates (AS); C10-C18 secondary (2,3) alkyl sulphates; C10-C18 alkyl alkoxy sulphates (AExS) wherein preferably x is from 1-30; C10-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; mid-chain branched alkyl sulphates as discussed inUS 6,020,303 andUS 6,060,443 ; mid-chain branched alkyl alkoxy sulphates as discussed inUS 6,008,181 andUS 6,020,303 ; modified alkylbenzene sulphonate (MLAS) as discussed inWO 99/05243 WO 99/05242 WO 99/05244 WO 99/05082 WO 99/05084 WO 99/05241 WO 99/07656 WO 00/23549 WO 00/23548
The paraffin sulphonates may be monosulphonates or disulphonates and usually are mixtures thereof, obtained by sulphonating paraffins of 10 to 20 carbon atoms. Preferred sulphonates are those of C12-18 carbon atoms chains and more preferably they are C14-17 chains. Paraffin sulphonates that have the sulphonate group(s) distributed along the paraffin chain are described inUS2,503,280 ;US2,507,088 ;US3, 260,744 ;US 3,372 188 and inDE 735 096 . - Alkyl glyceryl sulphonate surfactants and/or alkyl glyceryl sulphate surfactants generally used have high monomer content (greater than 60 wt% by weight of the alkyl glycerol sulphonate surfactant). As used herein "oligomer" includes dimer, trimer, quadrimer, and oligomers up to heptamers of alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant. Minimization of the monomer content may be from 0 wt% to about 60 wt%, from 0 wt% to about 55 wt%, from 0 wt% to about 50 wt%, from 0 wt% to about 30 wt%, by weight of the alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant present.
- The alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant for use herein include such surfactants having an alkyl chain length from C10-40, C10-22, C12-18, and C16-18. The alkyl chain may be branched or linear, wherein when present, the branches comprise a C1-4 alkyl moiety, such as methyl (C1) or ethyl (C2). Generally, the structures of suitable alkyl glyceryl sulphonate surfactant oligomers that may be used herein include (A) dimers; (B) trimers, and (C) tetramers:
- One of skill in the art will recognize that the counter-ion may be substituted with other suitable soluble cations other than the sodium shown above. R in the above structures (A)-(C) is from C10-40, C10-22, C12-18, and C16-18. The alkyl chain may be branched or linear, wherein when present, the branches comprise a C1-4 alkyl moiety, such as methyl (C1) or ethyl (C2). One of skill in the art will also recognize that the corresponding alkyl glyceryl sulphate surfactant oligomers may also have similar structures with the SO3 - moiety being an OSO3 - moiety.
- The alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant oligomer content may be between 40wt% and 100 wt%, 45 wt% and 100 wt%, 50 wt% and 100wt%, 70wt% and 100wt% by weight of the alkyl glycerol sulphonate surfactant and/or alkyl glyceryl sulphate surfactant. As used herein, the "oligomer content" means the sum of the alkyl glyceryl sulphonate surfactant oligomers and/or alkyl glyceryl sulphate surfactant oligomers, such as dimers, trimers, quadrimers, and above (heptamers) present in the alkyl glyceryl sulphonate surfactant and/or alkyl glyceryl sulphate surfactant. More specifically, as shown below in Table I, nonlimiting examples of alkyl glyceryl sulphonate surfactant oligomer content demonstrates the weight percent of oligomers present and the minimization of the monomer content of the alkyl glyceryl sulphonate surfactant. The alkyl glyceryl sulphonate surfactant is optionally present at a level of at least 10%, more preferably from 10% to 40% and most preferably from 10% to 30% by weight of the composition.
- An optional component used in the liquid detergent composition of the present invention is dialkyl sulfosuccinates. The dialkyl sulfosuccinates may be a C6-15 linear or branched dialkyl sulfosuccinate. The alkyl moieties may be symmetrical (i.e., the same alkyl moieties) or asymmetrical (i.e., different alkyl moieties). Preferably, the alkyl moiety is symmetrical. The dialkyl sulfosuccinates may be present in the liquid detergent composition from 0.5% to 10% by weight of the composition.
- Nonionic surfactants are generally considered as hydrophobic surfactants. Nonionic surfactant, when present, is comprised in a typical amount of from 0.1% to 20%, preferably 0.5% to 10% by weight of the liquid detergent composition. Suitable nonionic surfactants include the condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from 2 to 18 moles of ethylene oxide per mole of alcohol.
The number of mole of ethylene oxide per mole of alcohol is usually between 2 and 6 for more hydrophobic nonionic surfactants. Most suitable hydrophobic surfactants for grease cleaning are the solubilising nonionic surfactants described inUS 2005/0107275 published on May 19, 2005 by the Procter & Gamble Company, pages 2-3, paragraphs [0018] to [0031].
Also suitable are alkylpolyglycosides having the formula R2O(CnH2nO)t(glycosyl)x (formula (III)), wherein R2 of formula (III) is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n of formula (III) is 2 or 3, preferably 2; t of formula (III) is from 0 to 10, preferably 0; and x of formula (III) is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. - Also suitable are fatty acid amide surfactants having the formula (IV):
- Cationic surfactants, when present in the composition, are present in an effective amount, more preferably from 0.1 % to 20%, by weight of the liquid detergent composition. Suitable cationic surfactants are quaternary ammonium surfactants. Suitable quaternary ammonium surfactants are selected from the group consisting of mono C6-C16, preferably C6-C10 N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyehthyl or hydroxypropyl groups. Another preferred cationic surfactant is an C6-C18 alkyl or alkenyl ester of a quaternary ammonium alcohol, such as quaternary chlorine esters. More preferably, the cationic surfactants have the formula (V):
- Preferred ingredients for the liquid detergent compositions are amine oxides surfactants which typically herein may be comprised at a level of from 0.1% to 15% by weight, preferably from 3.0% to 10% by weight of the liquid detergent composition. The amine oxide may have a linear or mid-branched alkyl moiety.
- Linear amine oxides, for optional use herein, include water-soluble amine oxides containing one C8-18 alkyl moiety and 2 moieties selected from the group consisting of C1-3 alkyl groups and C1-3 hydroxyalkyl groups; water-soluble phosphine oxides containing one C10-18 alkyl moiety and 2 moieties selected from the group consisting of C1-3 alkyl groups and C1-3 hydroxyalkyl groups; and water-soluble sulfoxides containing one C10-18 alkyl moiety and a moiety selected from the group consisting of C1-3 alkyl and C1-3 hydroxyalkyl moieties.
- Preferred amine oxide surfactants have formula (VI):
- The linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides.
- As used herein "mid-branched" means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the α carbon from the nitrogen on the alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The total sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16. The number of carbon atoms for the one alkyl moiety (n1) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric. As used herein "symmetric" means that | n1 - n2 | is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt%, more preferably at least 75 wt% to 100 wt% of the mid-branched amine oxides for use herein.
- The amine oxide further comprises two moieties, independently selected from a C1-3 alkyl, a C1-3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups. Preferably the two moieties are selected from a C1-3 alkyl, more preferably both are selected as a C1 alkyl.
- Other suitable, non-limiting examples of amphoteric detergent surfactants that are optional in the present invention include amido propyl betaines and derivatives of aliphatic or heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group. Typically, when present, ampholytic surfactants comprise from about 0.01% to about 20%, preferably from about 0.5% to about 10% by weight of the liquid detergent composition.
- The composition used in the method of the present invention further comprises one or more alkoxylated polyethyleneimine polymer as defined in claim 1. It has been found that such an alkoxylated polyethyleneimine polymer provides an improvement in suds mileage both in soft and hard water. Therefore, when combined with the polymer of the present invention, a much stronger suds performance profile across water hardnesses is observed. The combination of the 2 polymers further provides excellent grease cleaning especially through the broad range of regular to baked-on grease.
- The composition to be used in the method of the present invention, comprises from 0.01 wt% to 10 wt%, preferably from 0.01 wt% to 2 wt%, more preferably from 0.1 wt% to 1.5 wt%, even more preferable from 0.2% to 1.5% by weight of the composition of an alkoxylated polyethyleneimine polymer.
- The alkoxylated polyethyleneimine polymer of the present composition has a polyethyleneimine backbone having from 400 to 10000 weight average molecular weight, preferably from 400 to 7000 weight average molecular weight, alternatively from 3000 to 7000 weight average molecular weight.
- These polyamines can be prepared for example, by polymerizing ethyleneimine in presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid.
- The alkoxylation of the polyethyleneimine backbone includes: (1) one or two alkoxylation modifications per nitrogen atom, dependent on whether the modification occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom on a polyalkoxylene chain having an average of 1 to 30 alkoxy moieties per modification, wherein the terminal alkoxy moiety of the alkoxylation modification is capped with hydrogen, a C1-C4 alkyl or mixtures thereof; (2) a substitution of one C1-C4 alkyl moiety or benzyl moiety and one or two alkoxylation modifications per nitrogen atom, dependent on whether the substitution occurs at a internal nitrogen atom or at an terminal nitrogen atom, in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom by a polyalkoxylene chain having an average of 1 to 40 alkoxy moieties per modification wherein the terminal alkoxy moiety is capped with hydrogen, a C1-C4 alkyl or mixtures thereof; or (3) a combination thereof.
-
-
- The alkoxylation modification of the polyethyleneimine backbone consists of the replacement of a hydrogen atom by a polyalkoxylene chain having an average of 1 to 30 alkoxy moieties, preferably from 5 to 20 alkoxy moieties. The alkoxy moieties are selected from ethoxy (EO), 1,2-propoxy (1,2-PO), 1,3-propoxy (1,3-PO), butoxy (BO), and combinations thereof. Preferably, the polyalkoxylene chain is selected from ethoxy moieties and ethoxy/propoxy block moieties. More preferably, the polyalkoxylene chain is ethoxy moieties in an average degree of from 5 to 15 and the polyalkoxylene chain is ethoxy/propoxy block moieties having an average degree of ethoxylation from 5 to 15 and an average degree of propoxylation from about 1 to 16. Most preferable the polyalkoxylene chain is the ethoxy/propoxy block moieties wherein the propoxy moiety block is the terminal alkoxy moiety block.
- Additionally, one may quaternize the polyethyleneimine backbone nitrogen atoms with alkylating agent such as alkyl sulfates, alkyl halides, benzyl sulfates, or benzyl halides resulting in permanent quaternisation. The degree of permanent quaternization may be from 0% to about 30% and even 60% of the polyethyleneimine backbone nitrogen atoms. It is preferred to have less than 30% of the polyethyleneimine backbone nitrogen atoms permanently quaternized.
-
- Another preferred polyethyleneimine has the general structure of formula (II):
- Heat to 80°C in a 2 L reactor 900 g of a 50 wt% aqueous solution of PEI 5000 (backbone molecular weight 5000) and strip with nitrogen thrice (until a pressure of 500 kPa (5 bar) is obtained). Increase the temperature to 90°C and add 461 g ethylene oxide until pressure rises to 500 kPa (5 bar). Remove the volatile components after 2 hours by stripping with nitrogen at 80°C or vacuum of 50 kPa (500 mbar) at 80°C. Collect 1345 g of a 68% aqueous solution, which contains PEI 5000 with 1 EO / NH
- Treat in a 2 1 reactor 362 g of a 68.5% aqueous solution from step (a) with 31 g of 40% aqueous solution of potassium hydroxide and 300g xylene and and strip with nitrogen thrice (until a pressure of 500 kPa (5 bar) is obtained). Remove water during a 4 hour time period at 170°C (under ascription of solvent). Add 753 g ethylene oxide at 120°C until pressure of 300 kPa (3 bar) is obtained. Stir for 3 hours at 120°C. Remove the solvent from the compound and strip with a water steam at 120°C for 3 hours. Collect 1000 g of a bright brownish viscous liquid (amine: 2.5448 mmol KOH/g; pH value 1%ig in water 11.2), which is the desired product (PEI 5000 - 7 EO / NH).
- Treat in a 2 1 reactor 163 g of a 68.4% the aqueous solution from step (a) with 13.9 g of 40% an aqueous solution of potassium hydroxide, heat to 70°C and strip with nitrogen thrice (until a pressure of 500 kPa (5 bar) is obtained). Remove water during a 4 hour time period at 120°C and vacuum of 1 kPa (10 mbar). Add 506 g ethylene oxide at 120°C until pressure of 800 kPa (8 bar) is obtained. Stir for 4 hours at 120°C. Strip with nitrogent 120°C. Add 519 g propylene oxide at 120°C until pressure of 800 kPa (8 bar) is obtained. Stir for 4 hours at 102°C. Remove volatile components by stripping with nitrogen at 80°C or vacuum of 50 kPa (500 mbar) at 80°C. Collect 1178 g of a bright brownish viscous liquid (amine titer: 0.9276 mmol KOH/g; pH value 1%ig in water 10.67), which is the desired product (PEI 5000 - 10 EO / NH - 7 PO / NH).
OR - Treat in a 2 1 reactor 137 g of a 68.7% the aqueous solution from (a) with 11.8 g of 40% aqueous solution of potassium hydroxide and 300 g xylene and strip with nitrogen thrice (until pressure of 500 kPa (5 bar)). Remove the water present over the next 4 hours while maintaining a temperature of 170°C (under ascription of solvent). Add 428 g of ethylene oxide at 120°C until pressure of 300 kPa (3 bar) is obtained and stir for 2 hours at 120°C. Strip with nitrogen at 120°C. Add 439 g propylene oxide at 120°C until pressure of 300 kPa (3 bar) is obtained. Stir for 3 hours at 120°C. Remove the solvent from the compound and strip with a water steam at 120°C for 3 hours. Collect 956 g of a bright brownish viscous liquid (amine titer: 0.9672 mmol KOH/g; pH value 1%ig in water 10.69), which is the desired product (PEI 5000 - 10 EO / NH - 7 PO / NH).
- 300 g of PEI5000 - 10 EO/NH - 7 PO/NH (example 2) under nitrogen atmosphere were heated to 60°C. Subsequent 7.3 g dimethyl sulfate were dropwise added. Temperature rose to 70°C and the mixture was stirred for 3 h. Reduction of amine titer (from 0.9672 mmol /g to 0.7514 mmol/g) showed a quaternation of 22% of N. 307 g of a brownish, viscous liquid are received, which is PEI 5000 - (10 EO - 7 PO) / NH - 22% quatted.
- In a 2 1 reactor 516 g of polyethylene imine 600 (molecular weight 600 g/mol) and 10.3 g water were stripped with nitrogen thrice (until pressure of 5 bar) and heated to 90°C. At 90°C 528 g ethylene oxide were added. After 1 h stirring at 90°C 1050 g of a liquid are received. Volatile components are removed by stripping with nitrogen or vacuum of 10 mbar at 90°C. The liquid contains PEI 600 with 1 EO / NH.
- In a 2 1 reactor 86 g of a liquid from a) were treated with 10.8 g of 40% aqueous solution of KOH, heated to 80°C and stripped with nitrogen thrice (until pressure of 5 bar). Water was removed during 2.5 h at 120°C and vacuum of 10 mbar. Subsequent reactor was flushed with nitrogen and 384 g ethylene oxide were added at 120°C and 2 h stirred at this temperature afterwards. Afterwards at 120°C 393 g propylene oxide were added at 120°C and 2 h stirred at this temperature. Volatile components are removed by stripping with nitrogen or vacuum of 500 mbar at 80°C. 865 g of a bright brownish viscous liquid are received (amine titer: 1.0137 mmol /g; pH value 1%ig in water 11.15), which is the desired product (PEI 600 - 10 EO/NH - 7 PO/NH).
- The optional presence of magnesium ions may be utilized in the detergent composition when the compositions are used in softened water that contains few divalent ions. When utilized, the magnesium ions preferably are added as a hydroxide, chloride, acetate, sulphate, formate, oxide or nitrate salt to the compositions of the present invention. When included, the magnesium ions are present at an active level of from 0.01% to 1.5%, preferably from 0.015% to 1%, more preferably from 0.025 % to 0.5%, by weight of the liquid detergent composition.
- The present compositions may optionally comprise a solvent. Suitable solvents include C4-14 ethers and diethers, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof. When present, the liquid detergent composition will contain from 0.01% to 20%, preferably from 0.5% to 20%, more preferably from 1% to 10% by weight of the liquid detergent composition of a solvent. These solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present.
- The liquid detergent compositions of the invention may optionally comprise a hydrotrope in an effective amount so that the liquid detergent compositions are appropriately compatible in water. Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulphonate, sodium, potassium and ammonium toluene sulphonate, sodium potassium and ammonium cumene sulphonate, and mixtures thereof, and related compounds, as disclosed in
U.S. Patent 3,915,903 . The liquid detergent compositions of the present invention typically comprise from 0% to 15% by weight of the liquid detergent composition of a hydrotropic, or mixtures thereof, preferably from 1% to 10%, most preferably from 3% to 6% by weight. - The compositions of the present invention may optionally contain a polymeric suds stabilizer. These polymeric suds stabilizers provide extended suds volume and suds duration of the liquid detergent compositions. These polymeric suds stabilizers may be selected from homopolymers of (N,N-dialkylamino) alkyl esters and (N,N-dialkylamino) alkyl acrylate esters. The weight average molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from 1,000 to 2,000,000, preferably from 5,000 to 1,000,000, more preferably from 10,000 to 750,000, more preferably from 20,000 to 500,000, even more preferably from 35,000 to 200,000. The polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulphate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
-
- When present in the compositions, the polymeric suds booster may be present in the composition from 0.01% to 15%, preferably from 0.05% to 10%, more preferably from 0.1% to 5%, by weight of the liquid detergent composition.
- Another optional ingredient of the compositions according to the present invention is a diamine. Since the habits and practices of the users of liquid detergent compositions show considerable variation, the composition will preferably contain 0% to 15%, preferably 0.1% to 15%, preferably 0.2% to 10%, more preferably 0.25% to 6%, more preferably 0.5% to 1.5% by weight of said composition of at least one diamine.
- Preferred organic diamines are those in which pK1 and pK2 are in the range of 8.0 to 11.5, preferably in the range of 8.4 to 11, even more preferably from 8.6 to 10.75. Preferred materials include 1,3-bis(methylamine)-cyclohexane (pKa=10 to 10.5), 1,3 propane diamine (pK1=10.5; pK2=8.8), 1,6 hexane diamine (pK1=11; pK2=10), 1,3 pentane diamine (DYTEK EP®) (pK1=10.5; pK2=8.9), 2-methyl 1,5 pentane diamine (DYTEK A®) (pK1=11.2; pK2=10.0). Other preferred materials include primary/primary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diamines are preferred over secondary and tertiary diamines.
Definition of pK1 and pK2 - As used herein, "pKa1" and "pKa2" are quantities of a type collectively known to those skilled in the art as "pKa" pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa's can be obtained from relevant company literature, such as information supplied by DUPONT®, a supplier of diamines. As a working definition herein, the pKa of the diamines is specified in an all-aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M. - The liquid detergent compositions according to the present invention may comprise a linear or cyclic carboxylic acid or salt thereof to improve the rinse feel of the composition. The presence of anionic surfactants, especially when present in higher amounts in the region of 15-35% by weight of the composition, results in the composition imparting a slippery feel to the hands of the user and the dishware. This feeling of slipperiness is reduced when using the carboxylic acids as defined herein i.e. the rinse feel becomes draggy.
- Carboxylic acids useful herein include C1-6 linear or at least 3 carbon containing cyclic acids. The linear or cyclic carbon-containing chain of the carboxylic acid or salt thereof may be substituted with a substituent group selected from the group consisting of hydroxyl, ester, ether, aliphatic groups having from 1 to 6, more preferably 1 to 4 carbon atoms, and mixtures thereof.
- Preferred carboxylic acids are those selected from the group consisting of salicylic acid, maleic acid, acetyl salicylic acid, 3 methyl salicylic acid, 4 hydroxy isophthalic acid, dihydroxyfumaric acid, 1,2, 4 benzene tricarboxylic acid, pentanoic acid and salts thereof and mixtures thereof. Where the carboxylic acid exists in the salt form, the cation of the salt is preferably selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.
- The carboxylic acid or salt thereof, when present, is preferably present at the level of from 0.1% to 5%, more preferably from 0.2% to 1% and most preferably from 0.25% to 0.5%.
- Preferably, the liquid detergent compositions herein are formulated as clear liquid compositions. By "clear" it is meant stable and transparent. In order to achieve clear compositions, the use of solvents and hydrotropes is well known to those familiar with the art of light-duty liquid dishwashing compositions. Preferred liquid detergent compositions in accordance with the invention are clear single phase liquids, but the invention also embraces clear and opaque products containing dispersed phases, such as beads or pearls as described in
US 5,866,529, to Erilli, et al. , andUS 6,380,150, to Toussaint, et al. , provided that such products are physically stable (i.e., do not separate) on storage. - The liquid detergent compositions of the present invention may be packages in any suitable packaging for delivering the liquid detergent composition for use. Preferably the package is a clear package made of glass or plastic.
- The liquid detergent compositions herein can further comprise a number of other optional ingredients suitable for use in liquid detergent compositions such as perfume, dyes, opacifiers, enzymes, chelants, thickening agents and pH buffering means so that the liquid detergent compositions herein generally have a pH of from 4 to 14, preferably 6 to 13, most preferably 6 to 10. A further discussion of acceptable optional ingredients suitable for use in light-duty liquid detergent composition may be found in
US 5,798,505 . - The viscosity of the composition of the present invention is measured on a Brookfield viscometer model # LVDVII+ at 20 °C. The spindle used for these measurements is S31 with the appropriate speed to measure products of different viscosities; e.g., 12rpm to measure products of viscosity greater than 1000cps; 30 rpm to measure products with viscosities between 500cps - 1000 cps; 60 rpm to measure products with viscosities less than 500cps.
-
Table A - Light-Duty Liquid Dishwashing Detergent Composition Composition A* B C* D* E* F G* H* I C12-13AExS 1 29.0 26.0 26.0 26.0 29.0 29.0 15.0 5.0 15.0 C10-14 Amine Oxide 6.0 6.0 6.0 6.0 6.0 6.0 5.0 1.0 5.0 C11E9 Nonionic 2 - 2.0 2.0 - - - - 2.0 - LAS - - 2.0 - - - 14.0 13.0 14.0 PEG-grafted PVAc6 0.1 0.5 1.0 2.0 1.0 1.0 1.0 0.5 1.0 Solvents including Ethanol, NaCl and or polypropylene glycol 3.5 2.8 3.5 2.8 3.5 3.5 5.5 3.0 5.5 1.3 BAC Diamine 3 0.2 0.2 0.2 0.2 0.2 0.2 - - - Suds boosting polymer4 0.1 0.1 0.1 0.1 0.1 0.1 - - - alkoxylated polyethyleneimine polymer5 - 1.0 - - - 0.8 - - 0.8 Water and minors Balance * outside the claimed range
1: C12-13alkyl ethoxy sulphonate containing an average of 0.5 -3 ethoxy groups.
2: Nonionic may be either C11 Alkyl ethoxylated surfactant containing 9 ethoxy groups or C10 alkly ethoxylated surfactant containing 8 ethoxy groups.
3: 1.3. BAC is 1,3 bis(methylamine)-cyclohexane.
4: (N.N-dimethylamino)ethyl methacrylate homopolymer.
5: alkoxylated polyethyleneimine polymer, PEI600 with 10 exthoxy moieties (EO) and 7 propoxy moieties (PO) per nitrogen of the polyethyleneiminie backbone (NH) (example 4) and or a polymer as described above in examples 1-3.
6: An amphiphilic graft polymer or any mixture of polymers as defined below (i) to (iii) or exemplified according to any of following Examples 1, 2, 3, 4, 5 or 6 below. - (i) A 6,000 g/mol Mw polyethylene glycol backbone grafted at 70 °C with 60% vinyl acetate by weight of the resulting polymer.
- (ii) A 6,000 g/mol Mw polyethylene glycol backbone grafted at 70 °C with 60% vinyl acetate by weight of the resulting polymer, and 40% of ester links hydrolyzed.
- (iii) A 12,000 g/mol Mw polyethylene glycol backbone grafted at 70 °C with 54% vinyl acetate and 6% butyl acrylate by weight of the resulting polymer.
- The following 6 amphiphilic graft polymers may be prepared as follows. The K values may be measured in 3% by weight aqueous NaCl solution at 23°C and a polymer concentration of 1% by weight. The mean molar masses and polydispersities are determined by gel permeation chromatography using a 0.5% by weight LiBr solution in dimethylacetamide as the eluent and of polymethyl methacrylate (PMMA) as the standard. The degrees of branching may be determined by 13C NMR spectroscopy in deuterated dimethyl sulfoxide from the integrals of the signals of the graft sites and the -CH2-groups of the polyethylene glycol. The values reported relate to all of the polyethylene glycol present in the product, i.e. including ungrafted polyethylene glycol, and correspond to the number of side chains present on average per polyethylene glycol.
- A polymerization vessel equipped with stirrer and reflux condenser is initially charged with 480 g of polyethylene glycol (Mn 12,000) under a nitrogen atmosphere and melted at 70°C.
- After addition of 16.0 g of vinyl acetate and 0.2 g of tert-butyl peroxypivalate, dissolved in 0.9 g of dipropylene glycol, and stirring for a further 5 minutes, 304 g of vinyl acetate within 6 h (feed 1) and 4.0 g of tert-butyl peroxypivalate, dissolved in 18 g of dipropylene glycol, within 7 h (feed 2) are metered in in parallel continuously with constant flow rates at internal temperature 70°C with stirring.
- After feed 2 has ended and the mixture has been stirred at 70°C for a further hour, 4.8 g of tert-butyl peroxypivalate, dissolved in 9.0 g of dipropylene glycol, are added in 3 portions at 70°C with further stirring for two hours in each case. In addition, 73 g of dipropylene glycol are added to lower the viscosity.
- Residual amounts of vinyl acetate are removed by vacuum distillation at 70°C. Subsequently, a solids content of 24.3% by weight is established by adding water.
- The resulting graft polymer has a K value of 28.4, a polydispersity of 1.8 (weight average molecular weight, Mw, 36,900, and number average molecular weight, Mn, 21,000) and a degree of branching of 0.8% (corresponds to 0.15 graft site/50 EO units).
- A polymerization vessel equipped with stirrer and reflux condenser is initially charged with 400 g of polyethylene glycol (Mn 9000) under a nitrogen atmosphere and melted at 85°C.
- After addition of 20.0 g of vinyl acetate and 0.25 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 0.9 g of dipropylene glycol, and stirring for a further 5 minutes, 380 g of vinyl acetate within 6 h (feed 1) and 5.0 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 18 g of dipropylene glycol, within 7 h (feed 2) are metered in in parallel continuously with constant flow rates at internal temperature 85°C with stirring.
- After feed 2 has ended and the mixture has been stirred at 85°C for a further hour, 6.0 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 9.0 g of dipropylene glycol, are added in 3 portions at 85°C with further stirring for two hours in each case. In addition, 73 g of dipropylene glycol are added to lower the viscosity.
- Residual amounts of vinyl acetate are removed by vacuum distillation at 85°C. Subsequently, a solids content of 23.2% by weight is established by adding water.
- The resulting graft polymer has a K value of 24.0, a polydispersity of 1.9 (Mw 37 000, Mn 19 500) and a degree of branching of 0.8% (corresponds to 0.20 graft site/50 EO units).
- A polymerization pressure vessel equipped with stirrer and reflux condenser is initially charged with 1000 g of polyethylene glycol (Mn 6000) under a nitrogen atmosphere and melted at 90°C. Then, 1500 g of vinyl acetate within 6 h (feed 1) and 14.5 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 60.5 g of tripropylene glycol, within 7 h (feed 2) are metered in parallel continuously with constant flow rates at internal temperature 90°C with stirring.
- After feed 2 has ended and the mixture has been stirred at 90°C for a further hour, 17.1 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 22.6 g of tripropylene glycol, are added in 3 portions at 90°C with further stirring for two hours in each case. In addition, 73 g of dipropylene glycol are added to lower the viscosity.
- Residual amounts of vinyl acetate are removed by vacuum distillation at 90°C. Subsequently, a solids content of 22.8% by weight is established by adding water.
- The resulting graft polymer has a K value of 19.6, a polydispersity of 1.9 (Mw 35,700, Mn 18,800) and a degree of branching of 0.9% (corresponds to 0.33 graft site/50 EO units).
- A polymerization vessel equipped with stirrer and reflux condenser is initially charged with 480 g of polyethylene glycol (Mn 12,000) under a nitrogen atmosphere and melted at 70°C.
- After addition of 14.0 g of vinyl acetate, 1.6 g of butyl acrylate and 0.3 g of tert-butyl peroxypivalate, dissolved in 0.9 g of dipropylene glycol, and stirring for a further 5 minutes, 274 g of vinyl acetate within 6 h (feed 1), 30.4 g of butyl acrylate within 6 h (feed 2) and 6.0 g of tert-butyl peroxypivalate, dissolved in 18 g of dipropylene glycol, within 7 h (feed 3) are metered in in parallel continuously with constant flow rates at internal temperature 70°C with stirring.
- After feed 3 has ended and the mixture has been stirred at 70°C for a further hour, 7.2 g of tert-butyl peroxypivalate, dissolved in 9.0 g of dipropylene glycol, are added in 3 portions at 70°C with further stirring for two hours in each case. In addition, 73 g of dipropylene glycol are added to lower the viscosity.
- Residual amounts of monomer are removed by vacuum distillation at 70°C. Subsequently, a solids content of 19.8% by weight is established by adding water.
- The resulting graft polymer has a K value of 29.1, a polydispersity of 1.9 (Mw 35,500, Mn 18,400) and a degree of branching of 0.7% (corresponds to 0.13 graft site/50 EO units).
- A polymerization pressure vessel equipped with stirrer and reflux condenser is initially charged with 1175 g of polyethylene glycol (Mn 4000) under a nitrogen atmosphere and melted at 90°C.
- After addition of 88.0 g of vinyl acetate and 0.85 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 3.5 g of tripropylene glycol, and stirring for a further 5 minutes, 1674 g of vinyl acetate within 6 h (feed 1) and 17.0 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 71 g of tripropylene glycol, within 7 h (feed 2) are metered in in parallel continuously with constant flow rates at internal temperature 90°C with stirring.
- After feed 2 had ended and the mixture has been stirred at 90°C for a further hour, 39.0 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 21.0 g of tripropylene glycol, are added in 3 portions at 70°C with further stirring for two hours in each case. In addition, 73 g of dipropylene glycol are added to lower the viscosity.
- Residual amounts of vinyl acetate are removed by vacuum distillation at 90°C. Subsequently, a solids content of 23.4% by weight is established by adding water.
- The resulting graft polymer has a K value of 17.9, a polydispersity of 2.3 (Mw 26,800, Mn 11,700) and a degree of branching of 0.6% (corresponds to 0.33 graft site/50 EO units).
- A polymerization pressure vessel equipped with stirrer and reflux condenser is initially charged with 444 g of polyethylene glycol (Mn 6000) under a nitrogen atmosphere and melted at 90°C.
- After addition of 0.55 g of tert-butyl per-2-ethylhexanoate, dissolved in 1.7 g of tripropylene glycol, and stirring for a further 15 minutes, 666 g of vinyl acetate within 6 h (feed 1) and 7.22 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 21.6 g of tripropylene glycol, within 6.5 h (feed 2), and also, beginning 3 h after the start of feed 1, 233 g of alkoxylated 2-propylheptanol (1 mol of PO and 10 mol of EO/mol) within 3.5 h (feed 3) are metered in in parallel continuously with constant flow rates at internal temperature 90°C with stirring.
- After the end of feeds 2 and 3 and subsequent stirring at 90°C for a further hour, 6.1 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 18.25 g of tripropylene glycol, are added in 3 portions at 90°C with further stirring for two hours in each case.
- Residue amounts of vinyl acetate are removed by vacuum distillation at 90°C. Subsequently, a solids content of 86.9% by weight is established by adding water.
- The resulting graft polymer has K value of 17.6, a polydispersity of 1.8 (Mw 35,700, Mn 20,000) and a degree of branching of 0.9% (corresponds to 0.33 graft site/50 EO units).
Claims (17)
- A method of cleaning a dishware with a light duty liquid detergent composition comprising an amphiphilic graft polymer; said process comprising the steps of applying said composition onto said dishware, wherein said polymer is a random graft copolymer having a hydrophilic backbone comprising monomers selected from the group consisting of unsaturated C2-6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol, and mixtures thereof, and hydrophobic side chains selccted from the group comprising a C4-25 alkyl group, polypropylene; polybutylene, a vinyl ester of a saturated monocarboxylic acid containing from 1 to 6 carbon atoms; a C1-6 alkyl ester of acrylic or methacrylic acid; and a mixture thereof, and wherein the composition further comprise from 0.01% to 10% by weight of the composition of an alkoxylated polyethyleneimine polymer comprising a polyethyleneimine backbone having from about 400 to about 10000 weight average molecular weight and the alkoxylated polyethyleneimine polymer further comprises:(1) one or two alkoxylation medications per nitrogen atom of the polyethyleneimine backbone by a polyalkoxylene chain having an average of 1 to 30 alkoxy moieties per modification, wherein the terminal alkoxy moiety of the alkoxylation modification is capped with hydrogen, a C1-C4 alkyl or mixtures thereof;(2) a substitution of one C1-C4 alkyl moiety or a benzyl moiety and one or two alkoxylation modifications per nitrogen atom of the polyethyleneimine backbone by a polyalkoxylene chain having an average of 1 to 40 alkoxy moieties per modification wherein the terminal alkoxy moiety is capped with hydrogen, a C1-C4 alkyl or mixtures thereof, or(3) a combination thereof.
- A method of cleaning a dishware according to claim 1 wherein the polymer is further characterized as a random graft copolymer having a hydrophilic backbone comprising polyethylene glycol of molecular weight from 4,000 to 15,000, and from 50% to 65% by weight hydrophobic side chains formed by polymerising at least one monomer selected from a vinyl ester of a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and/or a C1-6 alkyl ester of acrylic or methacrylic acid.
- A method of cleaning a dishware according to claim 2 wherein the polymer is further characterized as a random graft copolymer having a hydrophilic backbone comprising polyethylene glycol of molecular weight from 4,000 to 15,000, and from 50% to 65% by weight hydrophobic side chains formed by polymerising at least one monomer selected from vinyl acetate, vinyl propionate and/or butyl acrylate.
- A method of cleaning a dishware according to claim 1 wherein the graft polymer is further characterized by being based on water-soluble polyalkylene oxides comprising alkylene oxide units (A) as a backbone and side chains formed by polymerization of a vinyl ester component (B), said polymer having an average of ≤ 1 graft site per 50 alkylene oxide units and mean molar masses Mw of from 3000 to 100 000.
- A method of cleaning a dishware according to claim 4 wherein the graft polymer has a polydispersity Mw/Mn of ≤ 3.
- A method of cleaning a dishware according to claims 4-5 wherein the graft polymer comprises ≤ 10% by weight of polyvinyl ester (B) in ungrafted form.
- A method of cleaning a dishware according to claims 4-6 wherein the graft polymer has(A) from 20% to 70% by weight of a water-soluble polyalkylene oxide as a backbone and(B) side chains formed by free-radical polymerization of from 30% to 80% by weight of a vinyl ester component composed of(B1) from 70% to 100% by weight of vinyl acetate and/or vinyl propionate and(B2) from 0 to 30% by weight of a further ethylenically unsaturated monomerin the presence of (A).
- A method of cleaning a dishware according to claim 4 wherein the graft polymer is an amphiphilic graft polymer obtainable by free-radical polymerization of(B) from 30% to 80% by weight of a vinyl ester component composed ofin the presence of(B1) from 70% to 100% by weight of vinyl acetate and/or vinyl propionate and(B2) from 0 to 30% by weight of a further ethylenically unsaturated monomer,(A) from 20% to 70% by weight of a water-soluble polyalkylene oxide of mean molar mass Mn of from 1500 to 20 000,(C) from 0.25% to 5% by weight, based on component (B), of a free radical-forming initiator, and(D) from 0 to 40% by weight, based on the sum of components (A), (B) and (C), of an organic solventat a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, is polymerized in such a way that the fraction of unconverted graft monomer (B) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the polyalkylene oxide (A).
- A method of cleaning a dishware according to any of the preceding claims, wherein 0.01ml to 150ml ofsaid liquid detergent composition is diluted in 2000ml to 20000ml water, and the dishware is immersed in the diluted composition thus obtained and cleaned by contacting the soiled surface of the dishware with a cloth, a sponge or a similar article.
- A method of cleaning a dishware according to claims 1-8, wherein the dishware is immersed in a water bath or held under running water and an effective amount of a liquid detergent composition is absorbed onto a device, and the device with the absorbed liquid detergent composition is contacted individually to the surface of each of the soiled dishware
- A method of cleaning a dishware according to any of the preceding claims wherein the composition comprises 1.0% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 25% to 40% by weight preferably from 30% to 38% of one or more surfactants by weight of the total composition.
- A method of cleaning a dishware according to any of the preceding claims wherein the composition comprises at least 5%, preferably from 5% to 40% and more preferably from 15% to 30% and even more preferably at 15% to 25% by weight of one ore more anionic surfactants by weight of the total composition.
- A method of cleaning a dishware according to claim 12 wherein the anionic surfactant is selected from the group consisting of an anionic sulphonate surfactant, an anionic sulphate surfactant and mixtures thereof; preferably selected from linear alkyl sulphonate, paraffin sulphonate; fatty alcohol sulphate, alkyl alkoxylated sulphate, and mixtures thereof; more preferably selected from linear alkyl sulphonate and/or paraffin sulphonate, even more preferably is linear alkyl sulphonate.
- A method of cleaning a dishware according to any of the preceding claims wherein the composition further comprises from 0.1% to 15% by weight of the liquid detergent composition of an amine oxide.
- A method of cleaning a dishware according to claim 15 wherein the alkoxylation modifications are selected from ethoxy moieties (EO), 1,2-propoxy moieties (1,2-PO), 1,3-propoxy moieties (1,3-PO), butoxy moieties (BO), and combinations thereof.
- A method of cleaning a dishware according to any of the preceding claims wherein the alkoxylation modifications are selected from ethoxy moieties, ethoxy/propoxy block moieties
- A method of cleaning a dishware according to any of the preceding claims wherein the alkoxylation modifications are ethoxy/propoxy block moieties having an average degree of ethoxylation 5 to 15 and an average degree of propoxylation from 1 to 16.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08156229A EP2014755B1 (en) | 2007-05-29 | 2008-05-15 | Method of cleaning dishware |
US12/128,284 US7998279B2 (en) | 2007-05-29 | 2008-05-28 | Liquid detergent composition comprising an amphiphilic graft polymer |
US13/176,934 US8784571B2 (en) | 2007-05-29 | 2011-07-06 | Liquid detergent composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07109087 | 2007-05-29 | ||
EP07111413 | 2007-06-29 | ||
EP08156229A EP2014755B1 (en) | 2007-05-29 | 2008-05-15 | Method of cleaning dishware |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2014755A2 EP2014755A2 (en) | 2009-01-14 |
EP2014755A3 EP2014755A3 (en) | 2009-03-25 |
EP2014755B1 true EP2014755B1 (en) | 2012-03-21 |
Family
ID=39720143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08156229A Revoked EP2014755B1 (en) | 2007-05-29 | 2008-05-15 | Method of cleaning dishware |
Country Status (8)
Country | Link |
---|---|
US (2) | US7998279B2 (en) |
EP (1) | EP2014755B1 (en) |
JP (1) | JP2010528170A (en) |
AT (1) | ATE550417T1 (en) |
CA (1) | CA2688552A1 (en) |
ES (1) | ES2384588T3 (en) |
MX (1) | MX2009012894A (en) |
WO (1) | WO2008146194A1 (en) |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2115023B1 (en) * | 2007-03-05 | 2012-01-04 | Basf Se | Polyamine-polyacrylate dispersant |
ATE550417T1 (en) * | 2007-05-29 | 2012-04-15 | Procter & Gamble | METHOD FOR CLEANING DISHES |
WO2009005737A1 (en) * | 2007-06-29 | 2009-01-08 | The Procter & Gamble Company | Laundry detergent compositions comprising amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
CN101848984B (en) * | 2007-11-09 | 2012-05-30 | 宝洁公司 | Cleaning compositions with amphiphilic water-soluble polyalkylenimines having an inner polyethylene oxide block and an outer polypropylene oxide block |
RU2536470C2 (en) * | 2009-02-12 | 2014-12-27 | Геркулес Инкорпорейтед | Water-based composition for application for personal hygiene, in everyday life and in organisations |
JP5637678B2 (en) * | 2009-11-17 | 2014-12-10 | 株式会社日本触媒 | NOVEL POLYMER AND PROCESS FOR PRODUCING THE SAME |
US8334250B2 (en) * | 2009-12-18 | 2012-12-18 | The Procter & Gamble Company | Method of making granular detergent compositions comprising amphiphilic graft copolymers |
US20110152161A1 (en) * | 2009-12-18 | 2011-06-23 | Rohan Govind Murkunde | Granular detergent compositions comprising amphiphilic graft copolymers |
US20110288181A1 (en) * | 2010-05-21 | 2011-11-24 | Basf Se | Preparations of biologically active substances with enlarged surface based on amphiphilic copolymers |
CN102905695A (en) * | 2010-05-21 | 2013-01-30 | 巴斯夫欧洲公司 | Preparations of biologically active substances with enlarged surface area based on amphiphilic copolymers |
US20130150276A1 (en) * | 2011-12-09 | 2013-06-13 | The Procter & Gamble Company | Method of providing fast drying and/or delivering shine on hard surfaces |
WO2013134601A1 (en) * | 2012-03-09 | 2013-09-12 | The Procter & Gamble Company | Detergent compositions comprising graft polymers having broad polarity distributions |
US8754027B2 (en) | 2012-05-11 | 2014-06-17 | Basf Se | Quaternized polyethulenimines with a high ethoxylation degree |
US9068147B2 (en) | 2012-05-11 | 2015-06-30 | Basf Se | Quaternized polyethylenimines with a high quaternization degree |
MX2014013743A (en) * | 2012-05-11 | 2015-09-16 | Basf Se | Quaternized polyethylenimines with a high quaternization degree. |
US8623806B2 (en) * | 2012-05-11 | 2014-01-07 | The Procter & Gamble Company | Liquid detergent composition for improved shine |
PL2847251T3 (en) * | 2012-05-11 | 2017-09-29 | Basf Se | Quaternized polyethylenimines with a high ethoxylation degree |
US9951303B2 (en) | 2012-10-02 | 2018-04-24 | Robertet, Inc. | Compositions for grafting fragrance substances |
KR20150126634A (en) | 2013-02-28 | 2015-11-12 | 바스프 에스이 | Aqueous formulations, their manufacture, and their use in hard surface cleaning |
EP2832843B1 (en) | 2013-07-30 | 2019-08-21 | The Procter & Gamble Company | Method of making granular detergent compositions comprising polymers |
ES2713084T3 (en) | 2013-07-30 | 2019-05-17 | Procter & Gamble | Method for preparing granular detergent compositions comprising surfactants |
EP3162880A1 (en) * | 2015-10-29 | 2017-05-03 | The Procter and Gamble Company | Liquid detergent composition |
EP3239282B1 (en) * | 2016-04-27 | 2018-08-29 | The Procter and Gamble Company | Method of manual dishwashing |
EP3645691A1 (en) * | 2017-06-08 | 2020-05-06 | The Procter and Gamble Company | Non-homogeneous compositions |
EP3489335B1 (en) * | 2017-11-27 | 2020-08-19 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
CA3081829A1 (en) | 2017-11-27 | 2019-05-31 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
EP3489336B1 (en) * | 2017-11-27 | 2020-05-13 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
WO2019197315A1 (en) * | 2018-04-13 | 2019-10-17 | Basf Se | Process for cleaning dishware |
US11326129B2 (en) * | 2018-06-26 | 2022-05-10 | The Procter & Gamble Company | Fabric care compositions that include a graft copolymer and related methods |
EP3633016A1 (en) * | 2018-10-04 | 2020-04-08 | The Procter & Gamble Company | Liquid hand dishwashing cleaning composition |
US11186805B2 (en) | 2019-12-20 | 2021-11-30 | The Procter & Gamble Company | Particulate fabric care composition |
EP4134421A1 (en) * | 2021-08-12 | 2023-02-15 | The Procter & Gamble Company | Detergent composition comprising detersive surfactant and graft polymer |
US20230062984A1 (en) * | 2021-08-13 | 2023-03-02 | Henkel IP & Holding GmbH | Use of Polymer Blends To Reduce Or Eliminate Amine Oxide In Hand Dishwashing Detergents |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007138053A1 (en) * | 2006-05-31 | 2007-12-06 | Basf Se | Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
Family Cites Families (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE735096C (en) | 1940-12-09 | 1943-05-06 | Ig Farbenindustrie Ag | Process for the production of sulphonic acids |
US2503280A (en) | 1947-10-24 | 1950-04-11 | Du Pont | Azo catalysts in preparation of sulfonic acids |
US2507088A (en) | 1948-01-08 | 1950-05-09 | Du Pont | Sulfoxidation process |
FR1247957A (en) | 1958-09-28 | 1960-12-09 | Ajinomoto Kk | Process for the continuous separation of racemic amino acids |
US3372188A (en) | 1965-03-12 | 1968-03-05 | Union Oil Co | Sulfoxidation process in the presence of sulfur trioxide |
CA995092A (en) | 1972-07-03 | 1976-08-17 | Rodney M. Wise | Sulfated alkyl ethoxylate-containing detergent composition |
US5049302A (en) * | 1988-10-06 | 1991-09-17 | Basf Corporation | Stable liquid detergent compositions with enchanced clay soil detergency and anti-redeposition properties |
CA2029631A1 (en) * | 1989-11-22 | 1991-05-23 | Kathleen A. Hughes | Graft polymers as biodegradable detergent additives |
PE6995A1 (en) * | 1994-05-25 | 1995-03-20 | Procter & Gamble | COMPOSITION INCLUDING A PROPOXYLATED POLYKYLENE OAMINE POLYKYLENE OAMINE POLYMER AS DIRT SEPARATION AGENT |
KR0126719Y1 (en) | 1995-10-07 | 1998-10-01 | 김광호 | Microwave oven |
US5750483A (en) * | 1995-12-06 | 1998-05-12 | Basf Corporation | Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide |
EG21623A (en) | 1996-04-16 | 2001-12-31 | Procter & Gamble | Mid-chain branced surfactants |
PH11997056158B1 (en) | 1996-04-16 | 2001-10-15 | Procter & Gamble | Mid-chain branched primary alkyl sulphates as surfactants |
EG22088A (en) | 1996-04-16 | 2002-07-31 | Procter & Gamble | Alkoxylated sulfates |
KR100196425B1 (en) | 1996-05-16 | 1999-06-15 | 윤종용 | Method for controlling sound of multimedia display monitor |
US5866529A (en) | 1996-09-20 | 1999-02-02 | Colgate-Palmolive Co | High foaming nonionic surfactant base liquid detergent comprising gelatin beads |
WO1999005084A1 (en) | 1997-07-21 | 1999-02-04 | The Procter & Gamble Company | Process for making alkylbenzenesulfonate surfactants from alcohols and products thereof |
WO1999005241A1 (en) | 1997-07-21 | 1999-02-04 | The Procter & Gamble Company | Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof |
TR200000882T2 (en) | 1997-07-21 | 2000-09-21 | The Procter & Gamble Company | Improved process for making alkylbenzenesulfonate and products containing them. |
ES2195358T3 (en) | 1997-07-21 | 2003-12-01 | Procter & Gamble | DETERGENT COMPOSITIONS CONTAINING MIXTURES OF DISORGANIZED CRYSTALLINITY VOLTAGES. |
ID28110A (en) | 1997-07-21 | 2001-05-03 | Procter & Gamble | ALFYLBENZENASULFONATE SURFACTED ENHANCED |
PH11998001775B1 (en) | 1997-07-21 | 2004-02-11 | Procter & Gamble | Improved alkyl aryl sulfonate surfactants |
TR200000362T2 (en) | 1997-08-08 | 2000-07-21 | The Procter & Gamble Company | Processes developed for making surfactants by floating separation and products of these processes. |
FR2774694B1 (en) * | 1998-01-19 | 2003-08-08 | Rhodia Chimie Sa | USE OF COPOLYMERS BASED ON UNSATURATED ACIDS OR DERIVATIVES THEREOF AS FOAMENING AGENTS |
CA2346690C (en) | 1998-10-20 | 2003-12-16 | Jeffrey John Scheibel | Laundry detergents comprising modified alkylbenzene sulfonates |
AU763324B2 (en) | 1998-10-20 | 2003-07-17 | Procter & Gamble Company, The | Laundry detergents comprising modified alkylbenzene sulfonates |
US6380150B1 (en) | 2001-07-05 | 2002-04-30 | Colgate-Palmolive Company | Light duty liquid composition containing gelatin beads and polyacrylate thickener |
ATE431844T1 (en) * | 2002-02-11 | 2009-06-15 | Rhodia Chimie Sa | DETERGENT WITH BLOCK COPOLYMER |
US20050107275A1 (en) | 2003-11-14 | 2005-05-19 | Hecht Stacie E. | Liquid detergent composition comprising a solubilizing nonionic surfactant |
DE102004038072A1 (en) | 2004-07-28 | 2006-03-23 | Varta Microbattery Gmbh | Galvanic element |
ES2354269T3 (en) * | 2005-04-15 | 2011-03-11 | Basf Se | WATER SOLUBLE ALCOXYLATED WATER POLYCHYLEMINS WITH AN INTERNAL BLOCK OF POLYETHYLENE OXIDE AND AN EXTERNAL BLOCK OF POLYPROPYLENE OXIDE. |
WO2006130442A1 (en) * | 2005-05-31 | 2006-12-07 | The Procter & Gamble Company | Detergent composition |
EP1888734A2 (en) * | 2005-05-31 | 2008-02-20 | The Procter and Gamble Company | Polymer-containing detergent compositions and their use |
EP1896559B1 (en) * | 2005-06-29 | 2012-09-26 | The Procter and Gamble Company | Use of an effervescent product to clean soiled dishes by hand washing |
US7465701B2 (en) * | 2006-05-31 | 2008-12-16 | The Procter & Gamble Company | Detergent composition |
ATE550417T1 (en) | 2007-05-29 | 2012-04-15 | Procter & Gamble | METHOD FOR CLEANING DISHES |
-
2008
- 2008-05-15 AT AT08156229T patent/ATE550417T1/en active
- 2008-05-15 EP EP08156229A patent/EP2014755B1/en not_active Revoked
- 2008-05-15 ES ES08156229T patent/ES2384588T3/en active Active
- 2008-05-16 JP JP2010509924A patent/JP2010528170A/en not_active Ceased
- 2008-05-16 MX MX2009012894A patent/MX2009012894A/en active IP Right Grant
- 2008-05-16 WO PCT/IB2008/051936 patent/WO2008146194A1/en active Application Filing
- 2008-05-16 CA CA2688552A patent/CA2688552A1/en not_active Abandoned
- 2008-05-28 US US12/128,284 patent/US7998279B2/en not_active Expired - Fee Related
-
2011
- 2011-07-06 US US13/176,934 patent/US8784571B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007138053A1 (en) * | 2006-05-31 | 2007-12-06 | Basf Se | Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
Also Published As
Publication number | Publication date |
---|---|
CA2688552A1 (en) | 2008-12-04 |
EP2014755A3 (en) | 2009-03-25 |
ATE550417T1 (en) | 2012-04-15 |
EP2014755A2 (en) | 2009-01-14 |
ES2384588T3 (en) | 2012-07-09 |
JP2010528170A (en) | 2010-08-19 |
US7998279B2 (en) | 2011-08-16 |
WO2008146194A1 (en) | 2008-12-04 |
US20080300158A1 (en) | 2008-12-04 |
US8784571B2 (en) | 2014-07-22 |
MX2009012894A (en) | 2009-12-15 |
US20110259365A1 (en) | 2011-10-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2014755B1 (en) | Method of cleaning dishware | |
EP2021452B1 (en) | Liquid detergent composition for improved grease cleaning | |
CA2653880C (en) | Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters | |
JP5031309B2 (en) | Detergent composition for dishwasher | |
US8512480B2 (en) | Liquid detergent composition comprising a hydrophobically modified cellulosic polymer | |
WO2009007941A2 (en) | Liquid detergent composition | |
US20230087697A1 (en) | Biodegradable graft polymers | |
JP2020169330A (en) | Liquid detergent composition | |
CN111032844B (en) | Automatic dishwashing compositions containing dispersant polymers | |
WO2009093150A1 (en) | Liquid detergent composition | |
CN111278959A (en) | Dispersant polymers for automatic dishwashing formulations | |
JP2017510679A (en) | Novel copolymers useful in liquid detergent compositions | |
US20170096513A1 (en) | New copolymers useful in liquid detergent compositions | |
CN111971376A (en) | Automatic dishwashing composition with dispersant polymer | |
CN112739806A (en) | Automatic dishwashing composition with dispersant polymer | |
CN113906126A (en) | Dispersant polymers for automatic dishwashing | |
KR20180135894A (en) | A copolymer containing a polyalkylene oxide group and a quaternary nitrogen atom |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA MK RS |
|
17P | Request for examination filed |
Effective date: 20090916 |
|
17Q | First examination report despatched |
Effective date: 20091012 |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 550417 Country of ref document: AT Kind code of ref document: T Effective date: 20120415 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602008014226 Country of ref document: DE Effective date: 20120516 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2384588 Country of ref document: ES Kind code of ref document: T3 Effective date: 20120709 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20120321 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120621 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20120321 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120622 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 550417 Country of ref document: AT Kind code of ref document: T Effective date: 20120321 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120721 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120723 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120531 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
26 | Opposition filed |
Opponent name: COLGATE-PALMOLIVE COMPANY Effective date: 20121218 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120531 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120531 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20130131 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602008014226 Country of ref document: DE Effective date: 20121218 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120531 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120515 |
|
PLAF | Information modified related to communication of a notice of opposition and request to file observations + time limit |
Free format text: ORIGINAL CODE: EPIDOSCOBS2 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120621 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120321 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120515 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080515 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R103 Ref document number: 602008014226 Country of ref document: DE Ref country code: DE Ref legal event code: R064 Ref document number: 602008014226 Country of ref document: DE |
|
RDAF | Communication despatched that patent is revoked |
Free format text: ORIGINAL CODE: EPIDOSNREV1 |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
27W | Patent revoked |
Effective date: 20150122 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state |
Effective date: 20150122 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20150601 Year of fee payment: 8 Ref country code: ES Payment date: 20150512 Year of fee payment: 8 Ref country code: GB Payment date: 20150424 Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R107 Ref document number: 602008014226 Country of ref document: DE |